Preparation of Germyl Complexes of Osmium(II)

Abstract

The germyl complex Os[Ge 3 Cl 6 (OH) 2 ]P 4 (1) [P = P(OEt) 3 ] was prepared by allowing dihydride OsH 2 P 4 to react with GeCl 2 ·dioxane. Treatment of OsH 2 P 4 with GeCl 2 ·dioxane and then with SnCl 2 ·2H 2 O in ethanol yielded the mixed-li-Eur.

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 , , , …”

Iron, ruthenium and osmium

“…[OsH 2 Cl 2 (P i Pr 3 ) 2 ] reacts with HBcat forming the bis-boryl complex [OsH(Bcat) 2 Cl(P i Pr 3 ) 2 ] 120 whilst This journal is © The Royal Society of Chemistry 2013[OsH 2 (P(OEt) 3 ) 4 ] reacts with GeCl 2 Ádioxane forming an oxo-germanium cluster [Os(Ge 3 Cl 6 (OH) 2 )(P(OEt) 3 ) 4 ] 121. The reactions between [OsH 6 (P i Pr 3 ) 2 ] and nucleobases and nucleosides involves both N-H and N-C bond activation 122.…”