Oxidative-addition of germanium–hydrogen bonds to triosmium centers: Reactions of Os3(CO)10(μ-dppm) and Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) with Ph3GeH

Ruthenium and Osmium Germyl Complexes Derived from the Reactions of MXCl(PPh3)3 (M = Ru, Os; X = Cl, H) with Terphenylchlorogermylene (C6H3‐2,6‐Trip2)GeCl (Trip = 2,4,6‐iPr3C6H2)

“…A survey of the Cambridge Crystallographic Database for the Os–Ge bond lengths in terminal germyl complexes shows that the values fall in the range of 2.421–2.575 Å (a total of 13 complexes reported). [15d], [17a], [17b], [17c], [18b], , The Os(1)–Ge(1) bond length in 2 of 2.4424(8) Å is at the lower end of the values for the reported complexes: close to that of the Os IV –germyl complex {η 5 ‐C 5 H 4 ‐N(CH 2 CH=CH 2 ) 2 }OsH 2 (GePh 3 )(P i Pr 3 ) (2.45967 Å),[26a] but slightly shorter than the bond lengths observed in the Os IV –germyl complex (η 5 ‐C 5 H 5 )OsH(C≡CPh)(GePh 3 )(P i Pr 3 ) (2.50334 Å)[26b] and the cyclic osmium(II)–bis(germyl) complex Os[GeCl 2 (OH)GeCl 2 (OH)GeCl 2 ][P(OEt) 3 ] 4 [2.5047(15) Å and 2.5112(16) Å] …”

“…Closely related to germylene and germylyne complexes are transition‐metal germyl complexes, which have been known for a long time and have continuously received considerable attention over the last several decades, mainly because of their relevance to the catalytic transformations involving germanium, and materials chemistry. [12a], The most versatile methods for the synthesis of transition‐metal germyl complexes involve either oxidative addition of the Ge–X bond GeXR 3 (X = H, Cl)[12a], or insertion of dihalogen species GeX 2 into the M–X bond[12a], [13a], , to give triorgano M‐GeR 3 or trihalogen M‐GeX 3 germyl derivatives. However, despite of the large number of germyl complexes of transition metals that have been prepared in recent years, ruthenium germyl complexes are still much less common,[13a], [15c], , , while the osmium congeners are even more limited , , , …”

Reactions of Ru3(CO)10(μ-dppm) with Ph3GeH: Ge–H and Ge–C bond cleavage in Ph3GeH at triruthenium clusters

“…The resulting heterogeneous nanoparticle catalysts may be prepared by the deposition of a metal cluster containing a Group 14 ligand on an oxide support, yielding systems that exhibit high activity and selectivity for certain types of hydrogenation and dehydrogenation reactions [4]. We have been investigating the synthesis and structure of metal carbonyl complexes containing organogermanium and organotin ligands that can be used as precursors in the synthesis of such nanoscale catalysts during the last few years [5][6][7][8]. Ruthenium combined with the Group 14 elements, such as germanium or tin, continues to dominate the attention of different research groups with interest in catalysis [9][10][11].…”

“…Studies have shown that the incorporation of organogermanium/organotin moieties into the coordination sphere of a metal carbonyl cluster by oxidative addition of the corresponding hydrides R3EH (where E = Ge, Sn; R = alkyl, aryl) remains a convenient and widely used method for the synthesis of new Group 14-substituted metal clusters [6,7,[21][22][23][24]. Recently, we reported the preparation of new Os3Snx and Os3Gex clusters from the reactions of Os3(CO)10(μ-dppm) and the related ligand-activated cluster Os3(CO)8[μ3-Ph2PCH2P(Ph)C6H4](μ-H)with Ph3SnH [6] and Ph3GeH [7].…”

“…Studies have shown that the incorporation of organogermanium/organotin moieties into the coordination sphere of a metal carbonyl cluster by oxidative addition of the corresponding hydrides R3EH (where E = Ge, Sn; R = alkyl, aryl) remains a convenient and widely used method for the synthesis of new Group 14-substituted metal clusters [6,7,[21][22][23][24]. Recently, we reported the preparation of new Os3Snx and Os3Gex clusters from the reactions of Os3(CO)10(μ-dppm) and the related ligand-activated cluster Os3(CO)8[μ3-Ph2PCH2P(Ph)C6H4](μ-H)with Ph3SnH [6] and Ph3GeH [7]. This work reinforces the view that cluster degradation, which is frequently observed during the reaction between metal carbonyl clusters and organotin/organogermanium hydrides or other tin/germanium sources, may be significantly inhibited by the presence of a bridging dppm ligand that can impart additional stabilization to the metallic polyhedron by the ability to hold contiguous metal centers together.…”