E. Negishi, Magical Power of Transition Metals: Past, Present, and Future (Nobel Lecture), Angewandte Chemie International Edition, vol.50, pp.6738-6764, 2011.

A. Suzuki, Cross-Coupling Reactions Of Organoboranes: An Easy Way To Construct C-C Bonds (Nobel Lecture), Angewandte Chemie International Edition, vol.50, pp.6722-6737, 2011.

Y. O. Chauvin and . Metathesis, The Early Days (Nobel Lecture), vol.45, pp.3740-3747, 2006.

R. H. Grubbs, Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials

, Angewandte Chemie International Edition, vol.45, pp.3760-3765, 2006.

R. R. Schrock, Multiple Metal-Carbon Bonds for Catalytic Metathesis Reactions (Nobel Lecture), Angewandte Chemie International Edition, vol.45, pp.3748-3759, 2006.

W. A. Herrmann, M. Elison, J. Fischer, C. Köcher, and G. R. Artus, Metal Complexes of N-Heterocyclic Carbenes-A New Structural Principle for Catalysts in Homogeneous Catalysis, Angewandte Chemie International Edition, vol.34, pp.2371-2374, 1995.

A. Igau, H. Grutzmacher, A. Baceiredo, and G. Bertrand, Analogous .alpha.,.alpha.'-bis-carbenoid, triply bonded species: synthesis of a stable .lambda.3-phosphino carbene-.lambda.5-phosphaacetylene, Journal of the American Chemical Society, vol.110, pp.6463-6466, 1988.

Y. Mizuhata, T. Sasamori, and N. Tokitoh, Stable Heavier Carbene Analogues

, Chemical Reviews, vol.109, pp.3479-3511, 2009.

W. A. Herrmann, C. Köcher, and . Carbenes, Angewandte Chemie International Edition in English, vol.36, pp.2162-2187, 1997.

D. Bourissou, O. Guerret, F. P. Gabbaï, G. S. Bertrand, and . Carbenes, Chemical Reviews, vol.100, pp.39-92, 2000.

G. Trinquier, Double bonds and bridged structures in the heavier analogs of ethylene, Journal of the American Chemical Society, vol.112, pp.2130-2137, 1990.

E. Vessally, Singlet-triplet splitting and stability of divalent five-membered ring

C. C4h4m, C. Si, S. Ge, and P. , Heteroatom Chemistry, vol.19, pp.245-251, 2008.

W. Kutzelnigg, Chemical Bonding in Higher Main Group Elements, Angewandte Chemie International Edition in English, vol.23, pp.272-295, 1984.

. Chapter, General Introduction -88

L. Visscher and K. G. Dyall, Dirac-Fock atomic electronic structure calculations using different nuclear charge distributions. Atomic Data and Nuclear Data Tables, vol.67, pp.207-224, 1997.

T. Sasamori, N. Tokitoh, R. B. King, R. H. Crabtree, C. M. Lukehart et al., Group 14 Multiple Bonding, Encyclopedia of Inorganic Chemistry, 2006.

J. Satge, M. Massol, and P. Riviere, Divalent germanium species as starting materials and intermediates in organo germanium chemistry, Journal of Organometallic Chemistry, vol.56, pp.1-39, 1973.

W. P. Neumann, . Germylenes, and . Stannylenes, Chemical Reviews, vol.91, pp.311-334, 1991.

W. A. Herrmann, Stable Cyclic Germanediyls, Cyclogermylenes"): Synthesis, Structure, Metal Complexes, and Thermolyses, vol.31, pp.1485-1488, 1992.

T. Matsumoto, N. Tokitoh, and R. Okazaki, The First Kinetically Stabilized Germanethiones and Germaneselones: Syntheses, Structures, and Reactivities, Journal of the American Chemical Society, vol.121, pp.8811-8824, 1999.

W. P. Neumann and M. Schriewer, 7-Germanorbornadienes and their thermal cycloeliminations, Tetrahedron Letters, vol.21, p.4, 1980.

M. Schriewer, W. P. Neumann, and . Si, Chemistry of heavy carbene analogs R2M

S. Ge, Cheletropic cycloadditions of dimethylgermylene and diiodogermylene to conjugated dienes, Journal of the American Chemical Society, vol.8, pp.897-901, 1983.

N. Tokitoh, K. Kishikawa, T. Matsumoto, and R. Okazaki, Thermal Retrocycloaddition of Overcrowded Germirenes. A New Method for the Generation of Germylenes, Chemistry Letters, vol.24, pp.827-828, 1995.

N. Tokitoh, K. Kishikawa, and R. Okazaki, Synthesis and Structure of the First Germaketenedithioacetal, J. Chem. Soc., Chem. Commun, pp.1425-1426, 1995.

D. Lutters, C. Severin, M. Schmidtmann, and T. Müller, Activation of 7-Silanorbornadienes by N-Heterocyclic Carbenes: A Selective Way to

C. Silylenes, Journal of the American Chemical Society, vol.138, pp.6061-6067, 2016.

S. Collins, S. Murakami, J. T. Snow, and S. Masamune, Generation and reactivity of (where [(Mes)2 DAP] = {N(Mes)C(Me)}2CH), Inorganic Chemistry, vol.40, pp.1000-1005, 2001.

I. Saur, Search of Cationic Germanium(II)?Transition Metal Complexes L2Ge+ W(CO)5 and L2Ge+ W(CO)4 Ge+L2, vol.24, pp.2988-2996, 2005.
URL : https://hal.archives-ouvertes.fr/hal-00357899

I. Saur, S. Garcia-alonso, and J. Barrau, Three-coordinate divalent Group 14 element derivatives and related compounds, Applied Organometallic Chemistry, vol.19, pp.414-428, 2005.
URL : https://hal.archives-ouvertes.fr/hal-00353841

H. R. Dias and Z. Wang, Germanium-Containing Heterobicyclic 10-?-Electron Ring

, Synthesis and Characterization of Neutral and Cationic Germanium (II) Derivatives of Aminotroponiminates, Journal of the American Chemical Society, vol.119, pp.4650-4655, 1997.

A. E. Ayers, D. S. Marynick, and H. V. Dias, Azido Derivatives of Low-Valent Group 14 Elements: Synthesis, Characterization, and Electronic Structure of

. 2ati]gen3, Pr)2 ATI]SnN3 Featuring Heterobicyclic 10-?-Electron Ring Systems, Inorganic Chemistry, vol.39, pp.4147-4151, 2000.

R. K. Siwatch, S. Kundu, D. Kumar, S. Nagendran, and . Bulky-aminotroponiminate,

, Stabilized Germylene Monochloride and Its Alkyne Derivatives, Organometallics, vol.30, 1998.

D. Matioszek, From rational design of organometallic precursors to optimized synthesis of core/shell Ge/GeO2 nanoparticles, Dalton Trans, vol.44, pp.7242-7250, 2015.
URL : https://hal.archives-ouvertes.fr/hal-01503975

N. Nakata, S. Aoki, V. Y. Lee, and A. Sekiguchi, A Schrock-Type Germylene Complex: (?5-C5H4Et)2 (PMe3)Hf?Ge(SiMe tBu2)2, Organometallics, vol.34, pp.2699-2702, 2015.

J. Hlina, J. Baumgartner, C. Marschner, P. Zark, and T. Müller, Coordination Chemistry of Disilylated Germylenes with Group 4 Metallocenes, Organometallics, vol.32, pp.3300-3308, 2013.

C. Boehme, G. Frenking, and . N-heterocyclic-carbene, A Theoretical Study, Silylene, and Germylene Complexes of MCl (M = Cu, vol.17, pp.5801-5809, 1998.

Z. Benedek and T. Szilvási, Theoretical Assessment of Low-Valent Germanium Compounds as Transition Metal Ligands: Can They Be Better than Phosphines or NHCs?, Organometallics, vol.36, pp.1591-1600, 2017.

M. Lappert, J. Miles, P. Power, A. Carty, and N. Taylor,

, Bivalent Group 4B Heavy Metal Donors M[N(SiMe,),], (M = Ge or Pb) or Ge

, and the Crystal and Molecular Structure of [Cr(GO),(Ge{CH(SiMe3, vol.0, pp.458-459, 1977.

N. Tokitoh, K. Manmaru, and R. Okazaki, Synthesis and crystal structure of the first V. Notes and references 1

Y. Mizuhata, T. Sasamori, and N. Tokitoh, Stable Heavier Carbene Analogues

, Chemical Reviews, vol.109, pp.3479-3511, 2009.

L. Álvarez-rodríguez, J. A. Cabeza, P. García-Álvarez, and D. Polo, The transitionmetal chemistry of amidinatosilylenes, -germylenes and -stannylenes, Coordination Chemistry Reviews, vol.300, pp.1-28, 2015.

S. R. Foley, C. Bensimon, and D. S. Richeson, Facile Formation of Rare Terminal Chalcogenido Germanium Complexes with Alkylamidinates as Supporting Ligands, Journal of the American Chemical Society, vol.119, pp.10359-10363, 1997.

S. P. Green, C. Jones, P. C. Junk, K. Lippert, and A. Stasch, Synthetic, structural and theoretical studies of amidinate and guanidinate stabilised germanium(i) dimers

, Chemical Communications, vol.3978, p.3980, 2006.

C. Jones, R. P. Rose, and A. Stasch, Synthesis, characterisation and reactivity of germanium(ii) amidinate and guanidinate complexes, Dalton Transactions, pp.2871-2878, 2008.

L. Álvarez-rodríguez, J. A. Cabeza, P. García-Álvarez, E. Pérez-carreño, and . Polo,

D. Amidinatogermylene, Derivatives of Ruthenium Carbonyl: New Insights into the Reactivity of [Ru3(CO)12] with Two-Electron-Donor Reagents of High Basicity, Inorganic Chemistry, vol.54, pp.2983-2994, 2015.

H. Yeong, An Amidinate-Stabilized Germatrisilacyclobutadiene Ylide, Chemistry -A European Journal, vol.18, pp.2685-2691, 2012.

A. Brück, Pushing the ?-Donor Strength in Iridium Pincer Complexes

, Bis(silylene) and Bis(germylene) Ligands Are Stronger Donors than Bis(phosphorus(III))

. Ligands, Angewandte Chemie International Edition, vol.51, pp.11478-11482, 2012.

D. Gallego, From Bis(silylene) and Bis(germylene) Pincer-Type Nickel

, Complexes to Isolable Intermediates of the Nickel-Catalyzed Sonogashira Cross-Coupling Reaction, Journal of the American Chemical Society, vol.135, pp.15617-15626, 2013.

L. Álvarez-rodríguez, J. A. Cabeza, and J. M. Fernández-colinas,

D. Polo, Amidinatogermylene Metal Complexes as Homogeneous Catalysts in Alcoholic Media, Organometallics, vol.35, pp.2516-2523, 2016.

M. K. Sharma, D. Singh, P. Mahawar, R. Yadav, N. Selvarajan et al.,

, Cyanosilylation Using Germylene Stabilized Platinum(II) Dicyanide, Dalton Transactions, vol.47, pp.5943-5957, 2018.

I. Fernández and N. Khiar, Recent Developments in the Synthesis and Utilization of

, Chiral Sulfoxides. Chemical Reviews, vol.103, pp.3651-3706, 2003.

K. Omura and D. Swern, Oxidation of alcohols by "activated" dimethyl sulfoxide. a preparative, steric and mechanistic study, Tetrahedron, vol.34, pp.1651-1660, 1978.

Z. Wan, C. D. Jones, D. Mitchell, J. Y. Pu, and T. Y. Zhang, Practical Method for

, Transforming Alkynes into ?-Diketones, The Journal of Organic Chemistry, vol.71, pp.826-828, 2006.

R. Sanz, R. Aguado, M. R. Pedrosa, and F. J. Arnáiz, Simple and Selective Oxidation of Thiols to Disulfides with Dimethylsulfoxide Catalyzed by Dichlorodioxomolybdenum(VI), Synthesis, pp.856-858, 2002.

A. Castel, P. Rivière, J. Satgé, and M. Ahbala, Journal of Organometallic Chemistry, vol.328, pp.123-132, 1987.

. Roesky, The Chemistry of Aluminum(I), Silicon(II), and, organometallics, 2008.

, Germanium(II).pdf

M. El-ezzi, Iron Complexes with Stabilized Germylenes: Syntheses and Characterizations, Organometallics, vol.34, pp.571-576, 2015.
URL : https://hal.archives-ouvertes.fr/hal-02322286

L. Álvarez-rodríguez, J. A. Cabeza, P. García-Álvarez, and D. Polo,

A. Complexes, . Copper, . Silver, and . Gold, Organometallics, vol.34, pp.5479-5484, 2015.

J. Pospí?il, T. Pospí?il, and I. E. Markó, Sulfoxides in Julia?Lythgoe Olefination: Efficient and Stereoselective Preparation of Di-, Tri-, and Tetrasubstituted Olefins, Organic Letters, vol.7, pp.2373-2376, 2005.

G. Tsuchihashi, S. Iriuchijima, and K. Maniwa, Asymmetric synthesis using ?sulfinylcarbanions. II. Synthesis of optically active amines, Tetrahedron Letters, vol.14, pp.3389-3392, 1973.

S. Wolfe, L. A. Lajohn, and D. F. Weaver, On the structures of alpha-lithiated sulfoxide, sulfone and sulfonium systems. Implications for the stereochemistry of functionalization of carbon atoms adjacent to sulfur, Tetrahedron Letters, vol.25, pp.2863-2866, 1984.

Y. Peng, Reaction of Hydrogen or Ammonia with Unsaturated Germanium or Tin Molecules under Ambient Conditions: Oxidative Addition versus Arene Elimination, Journal of the American Chemical Society, vol.131, pp.16272-16282, 2009.

A. V. Zabula, F. E. Hahn, T. Pape, and A. Hepp, Preparation and Coordination Chemistry of Bidentate Benzimidazoline-2-germylenes, Organometallics, vol.26, pp.1972-1980, 2007.

O. Kühl, P. Lönnecke, and J. Heinicke, Formation and Structure of fac, p.3

, 2Ge) 3]: The First Structurally Characterized Group 6 Transition Metal Complex of an Unsaturated Diaminogermylene, Inorganic Chemistry, vol.42, pp.2836-2838, 2003.

F. Ullah, Transition Metal Complexes of N-Heterocyclic Germylenes, European Journal of Inorganic Chemistry, pp.221-229, 2009.

E. Alessio, Cis-and trans-dihalotetrakis (dimethyl sulfoxide) ruthenium (II) complexes

. X=-cl, Br): synthesis, structure, and antitumor activity, Inorganic chemistry, vol.27, pp.4099-4106, 1988.

H. Samouei, F. M. Miloserdov, E. C. Escudero-adán, and V. V. Grushin, (II) Complexes Used in Catalysis: A Reinvestigation, Organometallics, vol.33, pp.7279-7283, 2014.

J. A. Cabeza, J. M. Fernández-colinas, P. García-Álvarez, and D. Polo, Steric effects in the reactions of amidinate germylenes with ruthenium carbonyl: isolation of a coordinatively unsaturated diruthenium(0) derivative, RSC Adv, vol.4, pp.31503-31506, 2014.

L. Álvarez-rodríguez, J. A. Cabeza, P. García-Álvarez, and E. Pérez-carreño,

, Ruthenium Carbene Complexes Analogous to Grubbs-I Catalysts Featuring Germylenes as Ancillary Ligands, Organometallics, 2018.

J. Brugos, J. A. Cabeza, P. García-Álvarez, and E. Pérez-carreño, From a PGeP Pincer-Type Germylene to Metal Complexes Featuring Chelating (Ir) and Tripodal (Ir) PGeP Germyl and Bridging (Mn2) and Chelating (Ru) PGeP Germylene Ligands, Organometallics, vol.37, pp.1507-1514, 2018.

P. G. Hayes, R. Waterman, P. B. Glaser, and T. D. Tilley, Synthesis, Structure, and Reactivity of Neutral Hydrogen-Substituted Ruthenium Silylene and Germylene Complexes, Organometallics, vol.28, pp.5082-5089, 2009.

M. Calligaris, Structure and bonding in metal sulfoxide complexes, Coordination Chemistry Reviews, vol.153, pp.83-154, 1996.

J. M. Goicoechea, M. F. Mahon, M. K. Whittlesey, P. G. Kumar, and P. Pregosin,

, Dalton Transactions, pp.588-597, 2005.

M. D. Hargreaves, M. F. Mahon, and M. K. Whittlesey, Substitution Reactions, issue.1

B. Cardoso, P. De, B. Royo, and M. J. Calhorda, Preference for Sulfoxide S-or O-Bonding to 3d Transition Metals -DFT Insights, Journal of Organometallic Chemistry, vol.792, pp.167-176, 2015.

N. W. Alcock, J. M. Brown, P. L. Evans, . Phosphinosulphoxide-rhodium, and . Complexes,

C. Synthesis, C. Structure, and . Chemistry-of, ,3,5,6-r))-Bicyclo[2.2.1]-Hepta-2,5-Diene] [ P,O-Diphenyl( Phenylsulphinylmethyl) -Phosphine]Rhodium( I)Trif Luoromethanesulphonate and Asymmetric Analogues, Journal of Organometallic Chemistry, vol.356, issue.2, pp.233-247, 1988.

F. Lang, G. Chen, L. Li, J. Xing, F. Han et al., Rhodium-Catalyzed Highly Enantioselective Addition of Arylboronic Acids to 2-Nitrostyrenes by Tert

B. Ligand, Chemistry -A European Journal, vol.17, issue.19, pp.5242-5245, 2011.

S. Ogawa and N. Furukawa, Regiospecific Ortho Lithiation of O-Halophenyl p-Tolyl Sulfoxides and Synthesis of Meta-Substituted Optically Active Aryl Alcohols. The Journal of Organic Chemistry, vol.56, pp.5723-5726, 1991.

C. Quesnelle and T. Iihama, The Tert-Butyl Sulfoxide Directed Ortho Metalation Group

, New Synthetic Methodology for Substituted Aromatics and Pyridines and Comparisons with Others Metalation Directors, Tetrahedron Letters, vol.33, issue.19, pp.2625-2628, 1992.

, , pp.79042-79045

A. Szadkowska, A. Makal, K. Wo?niak, R. Kadyrov, K. R. Grela et al.,

, Metathesis Initiators Bearing Chelating Sulfoxide Ligands, vol.28, pp.2693-2700, 2009.

A. Szadkowska, K. ?ukowska, A. E. Pazio, K. Wo?niak, R. Kadyrov et al.,

, Ruthenium Olefin Metathesis Catalysts Containing Six-Membered Sulfone and Sulfonamide Chelating Rings, Organometallics, vol.30, issue.5, pp.1130-1138, 2011.

, Reaction of Sulfoxides with Diethylaminosulfur Trifluoride: Fluoromethyl Phenyl

, Sulfone, a Reagent for the Synthesis of Fluoroalkenes, Organic Syntheses, vol.9, issue.72, p.446, 1995.

A. Szadkowska, K. ?ukowska, A. E. Pazio, K. Wo?niak, R. Kadyrov et al.,

, Ruthenium Olefin Metathesis Catalysts Containing Six-Membered Sulfone and Sulfonamide Chelating Rings, Organometallics, vol.30, issue.5, pp.1130-1138, 2011.

F. A. Cotton, R. Francis, and W. D. Horrocks, Sulfoxides as Ligands. II. The InfraRed Spectra of Some Dimethyl Sulfoxide Complexes. The Journal of Physical Chemistry, vol.64, pp.1534-1536, 1960.

A. R. Davies, F. W. Einstein, N. P. Farrell, B. R. James, and R. S. Mcmillan,

P. Synthesis and X. , Structural Characterization of the Hexakis(Dimethyl Sulfoxide)Ruthenium(II) Cation. Inorganic Chemistry, vol.17, pp.1965-1969, 1978.

C. Jones, R. P. Rose, and A. Stasch, Synthesis

, Germanium(Ii) Amidinate and Guanidinate Complexes, Dalton Transactions, issue.21, pp.2871-2878, 2008.

D. Matioszek, N. Katir, N. Saffon, A. Castel, and . Halogermanium,

, Having Phenylamidinate As Supporting Ligands: Syntheses, Characterizations, and Reactivities, Organometallics, vol.2010, issue.13, pp.3039-3046

D. Matioszek, T. Kocsor, A. Castel, G. Nemes, J. Escudié et al.,

P. Germylenes and T. Gold,

, Chemical Communications, vol.48, issue.30, pp.3629-3631, 2012.

N. Tokitoh, K. Manmaru, and R. Okazaki, Synthesis and Crystal Structure of the First Base-Free Diarylgermylene-Transition Metal Mononuclear Complexes, Organometallics, vol.13, issue.1, pp.167-171, 1994.

A. V. Zabula, F. E. Hahn, T. Pape, and A. Hepp, Preparation and Coordination Chemistry of Bidentate Benzimidazoline-2-Germylenes, Organometallics, vol.26, issue.8, pp.1972-1980, 2007.

O. Kühl, P. Lönnecke, and J. Heinicke, Formation and Structure of Fac, p.3

, The First Structurally Characterized Group 6 Transition Metal Complex of an Unsaturated Diaminogermylene, Inorganic Chemistry, vol.42, issue.9, pp.2836-2838, 2003.

F. Ullah, O. Kühl, G. Bajor, T. Veszprémi, P. G. Jones et al., Transition Metal Complexes of N-Heterocyclic Germylenes, European Journal of Inorganic Chemistry, issue.2, pp.221-229, 2009.

E. Alessio, G. Mestroni, G. Nardin, W. M. Attia, M. Calligaris et al.,

C. Trans-dihalotetrakis, Dimethyl Sulfoxide) Ruthenium (II) Complexes

. X=-cl and . Br, Synthesis, Structure, and Antitumor Activity. Inorganic chemistry, vol.27, pp.4099-4106, 1988.

T. Tanase, T. Aiko, Y. Yamamoto, and . Diruthenium, II) Complex Containing an Unprecedented Bridging S,O-Bidentate Dimethyl Sulfoxide Ligand, Chemical Communications, issue.20, 1996.

S. Geremia, S. Mestroni, M. Calligaris, and E. Alessio, The First Example of a Double Bridged Diruthenium(II) Complex Containing the Rare Bridging S,O Bidentate Dimethyl Sulfoxide Ligand Which Defines a Stable Ru-Cl-Ru-S-O Five-Membered Ring, Journal of the Chemical Society, issue.15, pp.2447-2448, 1998.

E. Nakatani, Y. Takai, and H. Kurosawa, Coordination Behavior of Some Bridge Ligands Having S-O Bond Bound to Four-Membered Ring Unit (Ru2O2) of Dinuclear Areneruthenium Complexes, Journal of Organometallic Chemistry, vol.692, issue.1-3, pp.278-285, 2007.

Q. A. De-paula,

J. Ellena, E. E. Castellano, and A. A. Batista,

, Spectroscopic Investigation on the Formation of a Dinuclear Me2SO-Ru2-Mercaptopyridine Bridged Complex: [Ru2Cl3(µ-PyS)(µ-Dmso)(Dmso)4] · 2H2O, Journal of Chemical Crystallography, vol.39, issue.7, pp.519-524, 2009.

M. Calligaris, Structure and Bonding in Metal Sulfoxide Complexes: An Update. Coordination Chemistry Reviews, vol.248, pp.351-375, 2004.

L. Álvarez-rodríguez, J. A. Cabeza, J. M. Fernández-colinas, P. García-Álvarez, and D. Polo, Amidinatogermylene Metal Complexes as Homogeneous Catalysts in Alcoholic Media, Organometallics, vol.35, issue.15, pp.2516-2523, 2016.

J. A. Cabeza, J. M. Fernández-colinas, P. García-Álvarez, and D. Polo, Steric Effects in the Reactions of Amidinate Germylenes with Ruthenium Carbonyl: Isolation of a

, Coordinatively Unsaturated Diruthenium(0) Derivative. RSC Adv, vol.4, pp.31503-31506, 2014.

L. Álvarez-rodríguez, J. A. Cabeza, P. García-Álvarez, and E. Pérez-carreño,

, Ruthenium Carbene Complexes Analogous to Grubbs-I Catalysts Featuring Germylenes as

, Ancillary Ligands. Organometallics, 2018.

J. M. Goicoechea, M. F. Mahon, M. K. Whittlesey, and P. G. Kumar,

, Dalton Transactions, issue.3, pp.588-597, 2005.

M. D. Hargreaves, M. F. Mahon, and M. K. Whittlesey, Substitution Reactions of [Ru(Dppe)(CO)(H 2 O) 3 ][OTf] 2 . Inorganic Chemistry, vol.41, pp.3137-3145, 2002.

S. E. Flowers, M. C. Johnson, B. Z. Pitre, and B. M. Cossairt, Synthetic Routes to a

, Coordinatively Unsaturated Ruthenium Complex Supported by a Tripodal, Protic Bis(N-Heterocyclic Carbene) Phosphine Ligand, Dalton Transactions, vol.47, issue.4, pp.1276-1283, 2018.

T. Schaub, M. Backes, and U. Radius, Unusual Nickel-Mediated C-S Cleavage of Alkyl and Aryl Sulfoxides, Chem. Commun, issue.20, pp.2037-2039, 2007.

W. A. Herrmann, M. Denk, J. Behm, W. Scherer, F. Klingan et al., Cyclogermylenes"): Synthesis, Structure, Metal Complexes, and Thermolyses, vol.31, pp.1485-1488, 1992.

D. Gallego, A. Brück, E. Irran, F. Meier, M. Kaupp et al.,

, From Bis(Silylene) and Bis(Germylene) Pincer-Type Nickel(II) Complexes to Isolable Intermediates of the Nickel-Catalyzed Sonogashira Cross-Coupling Reaction, Journal

, , vol.135, pp.15617-15626, 2013.

M. Veith and L. Stahl, Novel Insertions of Carbene Homologues into Metal-N5-Cp Bonds: Sandwich Complexes with Ge2Ni and Sn2Ni Cores, Angewandte Chemie International Edition in English, vol.32, issue.1, pp.106-107, 1993.

K. E. Litz, J. E. Bender, J. W. Kampf, and M. M. Holl, Transition Metal Germylene Complexes as Hydrogenation Catalysts: The Synthesis of a Rare Bis

, Angewandte Chemie International Edition in English, vol.36, issue.5, pp.496-498, 1997.

. Germanium, Germanocene Dimeric Tricarbonyl

, Angewandte Chemie International Edition in English, vol.23, issue.1, pp.61-63, 1984.

D. L. Suess and J. C. Peters, Late-Metal Diphosphinosulfinyl S(O)P2 Pincer-Type Complexes, Organometallics, vol.2012, issue.15, pp.5213-5222

C. A. Tolman, Steric Effects of Phosphorus Ligands in Organometallic Chemistry and Homogeneous Catalysis, Chemical Reviews, vol.77, issue.3, pp.313-348, 1977.

D. J. Nelson and S. P. Nolan, Quantifying and Understanding the Electronic Properties of N-Heterocyclic Carbenes, Chemical Society Reviews, vol.42, issue.16, pp.6723-6753, 2013.

R. Dorta, E. D. Stevens, N. M. Scott, C. Costabile, L. Cavallo et al., Steric and Electronic Properties of N-Heterocyclic Carbenes (NHC): A Detailed Study on Their Interaction with Ni(CO)4, Journal of the American Chemical Society, vol.127, issue.8, pp.2485-2495, 2005.

A. Rosas-sánchez, I. Alvarado-beltran, A. Baceiredo, N. Saffon-merceron, S. Massou et al., Exceptionally Strong Electron-Donating Ability of Bora-Ylide Substituent Vis-à-Vis Silylene and Silylium Ion, Angewandte Chemie International Edition, vol.56, issue.35, pp.10549-10554, 2017.

S. Pelzer, B. Neumann, H. Stammler, N. Ignat'ev, and B. Hoge, The Bis(Pentafluoroethyl)Germylene Trimethylphosphane Adduct (C2F5)2 Ge

, Ligand Properties, and Reactivity, Angewandte Chemie International Edition, vol.55, issue.20, pp.6088-6092, 2016.

M. Baumeister and M. Denk, Donor Stabilized Germylenes and Their Transition Metal Complexes: Structure, Bonding, and Thermochemistry, Thesis, Master of Science, 2011.

Y. Mizuhata, T. Sasamori, and N. Tokitoh, Stable Heavier Carbene Analogues, Chemical Reviews, vol.109, issue.8, pp.3479-3511, 2009.

L. Álvarez-rodríguez, J. A. Cabeza, P. García-Álvarez, and D. Polo,

A. Complexes, . Copper, . Silver, and . Gold, Organometallics, vol.2015, issue.22, pp.5479-5484

W. P. Neumann, . Germylenes, and . Stannylenes, Chemical Reviews, vol.91, issue.3, pp.311-334, 1991.

M. M. Siddiqui, S. Sinhababu, S. Dutta, S. Kundu, P. N. Ruth et al.,

R. Irmer, D. Stalke, D. Koley, and H. W. Roesky, Silanylidene and Germanylidene Anions: Valence-Isoelectronic Species to the Well-Studied Phosphinidene, Angewandte Chemie International Edition, 2018.

T. Müller, P. Tholen, Z. Dong, and M. Schmidtmann,

, Aminoborole Complex of Germanium(II), Angewandte Chemie International Edition, 2018.

J. V. Dickschat, S. Urban, T. Pape, F. Glorius, and F. E. Hahn, Sterically Demanding and Chiral N,N?-Disubstituted N-Heterocyclic Germylenes and Stannylenes, pp.11519-11521, 2010.

H. Arii, F. Nakadate, K. Mochida, and T. Kawashima,

E. Germanium, II) Cation Bearing a Bis(Oxazoline) Ligand, Organometallics, vol.30, issue.17, pp.4471-4474, 2011.

J. Berthe, J. M. Garcia, E. Ocando, T. Kato, N. Saffon-merceron et al., Synthesis and Reactivity of a Phosphine-Stabilized Monogermanium Analogue of Alkynes, Journal of the American Chemical Society, vol.133, issue.40, pp.15930-15933, 2011.

J. M. García, E. Ocando-mavárez, T. Kato, D. S. Coll, and A. Briceño,

N. Merceron and A. Baceiredo, Synthesis and Characterization of Rhodium Complexes with Phosphine-Stabilized Germylenes, Inorganic Chemistry, vol.51, issue.15, pp.8187-8193, 2012.

H. Arii, M. Matsuo, F. Nakadate, K. Mochida, and T. Kawashima,

, Chiral Tin(Ii) Cation Bearing a Bis(Oxazoline) Ligand with Tetrahydrofuran Derivatives

, Dalton Transactions, vol.41, issue.36, 2012.

I. Piel, J. V. Dickschat, T. Pape, F. E. Hahn, and F. Glorius,

P. Derived and N. Stannylene, Dalton Transactions, vol.2012, issue.45, p.13788

P. K. Chinthakindi, T. Naicker, N. Thota, T. Govender, H. G. Kruger et al., Sulfonimidamides in Medicinal and Agricultural Chemistry, Angewandte Chemie, vol.56, issue.15, pp.4100-4109, 2017.

C. R. Johnson, E. U. Jonsson, and C. C. Bacon, Preparation and Reactions of Sulfonimidoyl Chlorides, The Journal of Organic Chemistry, vol.44, issue.13, pp.2055-2061, 1979.

M. R. Jones and D. J. Cram, Stereochemistry of Sulfur Compounds. VII. Course of Substitution at Sulfur Attached to Four Different Ligands, Journal of the American Chemical Society, vol.96, issue.7, pp.2183-2190, 1974.

C. Worch, A. C. Mayer, and C. Bolm, Synthesis and Use of Chiral Sulfoximines, Organosulfur Chemistry in Asymmetric Synthesis

T. Toru and C. Bolm, , pp.209-232, 2008.

F. W. Patureau, C. Worch, M. A. Siegler, A. L. Spek, C. Bolm et al., SIAPhos: Phosphorylated Sulfonimidamides and Their Use in Iridium-Catalyzed Asymmetric Hydrogenations of Sterically Hindered Cyclic Enamides. Advanced Synthesis & Catalysis, vol.354, pp.59-64, 2012.

O. I. Guzyr, L. N. Markovskii, M. I. Povolotskii, H. W. Roesky, and A. N. Chernega,

, Crystal Structure and NMR Studies of Bischelate Zinc Complex, Journal of Molecular Structure, vol.788, issue.1-3, pp.89-92, 2006.

E. Carl and D. Stalke, Germanium(II) and Tin(II) Halide Complexes Containing the Triimido Sulfur(VI) Phosphanyl Ligand: Germanium(II) and Tin(II) Halide Complexes

, European Journal of Inorganic Chemistry, issue.12, pp.2052-2056, 2015.

E. S. Levchenko, I. E. Sheinkman, A. V. Kirsanov, . Obshch, and . Kim, , vol.30, pp.1941-1946, 1960.

O. Garcia-mancheno and C. Bolm, Synthesis of Sulfonimidamides from Sulfinamides by Oxidation with N-Chlorosuccinimide, Beilstein Journal of Organic Chemistry, vol.3, issue.1, p.25, 2007.

J. Wen, H. Cheng, S. Dong, C. Bolm, S. Copper-catalyzed et al., Chemistry -A European Journal, vol.22, issue.16, pp.5547-5550, 2016.

F. Izzo, M. Schäfer, R. Stockman, U. Lücking, and . New, Practical One-Pot Synthesis of Unprotected Sulfonimidamides by Transfer of Electrophilic NH to Sulfinamides, vol.23, pp.15189-15193, 2017.

C. S. Richards-taylor, C. Martínez-lamenca, J. E. Leenaerts, A. A. Trabanco, and D. Oehlrich, The Synthesis of Trifluoromethyl-Sulfonimidamides from Sulfinamides. The Journal of Organic Chemistry, vol.82, pp.9898-9904, 2017.

Y. Chen and J. Gibson, A Convenient Synthetic Route to Sulfonimidamides from Sulfonamides, RSC Adv, vol.2015, issue.6, pp.4171-4174

B. Cetinkaya, I. Gumrukcu, M. F. Lappert, J. L. Atwood, R. D. Rogers et al., )2 (M = Ge or Sn), Tert-Butylphenoxides and the Crystal and Molecular Structures of M, vol.2, pp.2088-2089, 1980.

F. E. Hahn, A. V. Zabula, T. Pape, and A. Hepp, Preparation and Molecular Structures of Stable Bis(Germylenes) with Pincer Topology, European Journal of Inorganic Chemistry, issue.17, pp.2405-2408, 2007.

A. V. Zabula, F. E. Hahn, T. Pape, and A. Hepp, Preparation and Coordination Chemistry of Bidentate Benzimidazoline-2-Germylenes, Organometallics, vol.26, issue.8, pp.1972-1980, 2007.

D. Paul, F. Heins, S. Krupski, A. Hepp, C. G. Daniliuc et al., Synthesis and Reactivity of Intramolecularly NHC-Stabilized Germylenes and Stannylenes, vol.2017, pp.1001-1008

C. Jones, R. P. Rose, and A. Stasch, Synthesis

, Germanium(Ii) Amidinate and Guanidinate Complexes, Dalton Transactions, issue.21, pp.2871-2878, 2008.

O. A. Brusylovets, O. V. Vinichenko, A. I. Brusilovets, T. Lis, E. Bonnefille et al., New Substituents for the Stabilization of Low-Coordinate Germanium Species: Use in Access to Diazogermylenes, Polyhedron, vol.2010, issue.18, pp.3269-3276

D. Matioszek, N. Katir, N. Saffon, A. Castel, and . Halogermanium,

, Having Phenylamidinate As Supporting Ligands: Syntheses, Characterizations, and Reactivities, Organometallics, vol.2010, issue.13, pp.3039-3046

M. El-ezzi, T. Kocsor, F. -g.;-d'accriscio, D. Madec, S. Mallet-ladeira et al., Iron Complexes with Stabilized Germylenes: Syntheses and Characterizations, Organometallics, vol.34, issue.3, pp.571-576, 2015.
URL : https://hal.archives-ouvertes.fr/hal-02322286

N. Nakata, N. Hosoda, S. Takahashi, and A. Ishii, Chlorogermylenes and -Stannylenes Stabilized by Diimidosulfinate Ligands: Synthesis, Structures, and Reactivity, Hydrogen Transfer and Polymerization Catalysis, vol.47, pp.481-490, 2017.

, 3 mg) was dissolved in i-PrOH (X mL, see desired volume in table) and stirred for 10 min. Then, acetophenone (0.9 mmol, 105 µL) was added and the mixture stirred at the indicated temperature for the desired time. Aliquots (0.2 mL) were dissolved in CDCl 3 (0.4 mL) and conversions were determined by 1 H NMR analysis. Determination of ee was performed on a HPLC with a chiralcel OD column at a flow rate of 1 mL/min with a mobile phase of heptane/i--caprolactone: In a schlenk tube, vol.60

, Polymer was treated at the end of reaction by addition of benzoic acid. The mixture was then evaporated and the solid was then dissolved in DCM. The solution was cooled with liquid nitrogen and methanol was added drop

, Tetrahydrofuran was used as the eluent, and the flow rate was set up at 1.0 mL/min. A SHODEX precolumn (polystyrene AT806M/S Mw = 50000000 g/mol) and two STYRAGEL columns (HR1, 100-5000 g/mol, and HR 4E, 50-100000 g/mol) were used, The number-average and weight-average molar masses (Mn and Mw, respectively) and molar a R410 refractometer detector

Z. Benedek and T. Szilvási, Can Low-Valent Silicon Compounds Be Better Transition Metal Ligands than Phosphines and NHCs? RSC Advances, vol.5, pp.5077-5086, 2015.

A. Brück, D. Gallego, W. Wang, E. Irran, M. Driess et al., Pushing the ?

, Bis(Germylene) Ligands Are Stronger Donors than Bis(Phosphorus(III)) Ligands, Donor Strength in Iridium Pincer Complexes: Bis(Silylene) and, vol.2012, pp.11478-11482

D. Gallego, A. Brück, E. Irran, F. Meier, M. Kaupp et al.,

, From Bis(Silylene) and Bis(Germylene) Pincer-Type Nickel(II) Complexes to Isolable Intermediates of the Nickel-Catalyzed Sonogashira Cross-Coupling Reaction, Journal

, , vol.135, pp.15617-15626, 2013.

M. K. Sharma, D. Singh, P. Mahawar, R. Yadav, N. Selvarajan et al.,

, Cyanosilylation Using Germylene Stabilized Platinum(II) Dicyanide. Dalton Transactions, vol.47, pp.5943-5957, 2018.

D. Wang and D. Astruc, The Golden Age of Transfer Hydrogenation, Chemical Reviews, vol.115, issue.13, pp.6621-6686, 2015.

M. C. Carrión, F. Sepúlveda, F. A. Jalón, B. R. Manzano, and A. M. Rodríguez, Base-Free Transfer Hydrogenation of Ketones Using Arene Ruthenium

, Organometallics, vol.28, issue.13, pp.3822-3833, 2009.

D. G. Petra, P. C. Kamer, A. L. Spek, H. E. Schoemaker, and P. W. Van-leeuwen,

N. M. Aminosulf, Ox)Ides as Ligands for Iridium(I)-Catalyzed Asymmetric Transfer Hydrogenation, The Journal of Organic Chemistry, vol.65, issue.10, pp.3010-3017, 2000.

L. Tang, Q. Wang, J. Wang, Z. Lin, X. Wang et al.,

J. Deng, A New Chiral Sulfinyl-NH-Pyridine Ligand for Ir-Catalyzed Asymmetric Transfer Hydrogenation Reaction, Tetrahedron Letters, vol.53, issue.30, pp.3839-3842, 2012.

H. R. Kricheldorf, I. Kreiser-saunders, C. Boettcher, and . Polylactones, , p.31

. Sn, Ll)Octoate-Initiated Polymerization of L-Lactide: A Mechanistic Study, Polymer, vol.36, issue.6, pp.1253-1259, 1995.

C. Qi and Z. Wang, Synthesis and Characterization of Aluminum(III) and Tin

, Complexes Supported by Diiminophosphinate Ligands and Their Application in Ring-Opening Polymerization Catalysis of ?-Caprolactone, Journal of Polymer Science Part A: Polymer Chemistry, vol.44, issue.15, pp.4621-4631, 2006.

A. Dumitrescu, B. Martin-vaca, H. Gornitzka, J. Cazaux, D. Bourissou et al., Samarium(III) and Tin(II) Complexes Featuring a Tridentate Nitrogen Donor for the Ring-Opening Copolymerization of (D,L)-Lactide and Glycolide, European Journal of Inorganic Chemistry, issue.8, pp.1948-1951, 2002.

N. Nimitsiriwat, V. C. Gibson, E. L. Marshall, A. J. White, S. H. Dale et al., Single-Site Initiators for the Controlled Production of Polylactide, Tert-Butylamidinate Tin(Ii) Complexes: High Activity, p.4464, 2007.

F. W. Seidel, S. Frieß, F. W. Heinemann, A. Chelouan, A. Scheurer et al., Dorta, R. C2-Symmetric (SO)N(SO) Sulfoxide Pincer Complexes of Mg and Pd

, Helicity Switch by Ambidentate S/O-Coordination and Isolation of a Chiral Pd-Sulfenate

, Organometallics, vol.37, issue.7, pp.1160-1171, 2018.

J. A. Castro-osma, C. Alonso-moreno, J. C. García-martinez, J. Fernández-baeza, L. F. Sánchez-barba et al., Ring-Opening (ROP) versus Ring-Expansion (REP) Polymerization of ?-Caprolactone To Give Linear or Cyclic Polycaprolactones, Macromolecules, vol.2013, issue.16, pp.6388-6394