Synthesis and Reactivity of Germyl Complexes of Manganese and Rhenium

Trichlorogermyl complexes M(GeCl3)(CO)nP 5- n (1-4) [M = Mn, Re; n = 2, 3; P = PPh(OEt)2 (a), P(OEt)3 (b)] were prepared by allowing chloro compounds MCl(CO) nP5- n to react with an excess of GeCl2• dioxane in 1,2-dichloroethane. Treatment of compounds 1-4 with LiAlH4 in thf yielded trihydridegermyl derivatives M(GeH3)(CO) nP5-n (5-8), whereas treatment of the same complexes with NaBH4 in ethanol afforded triethoxygermyl derivatives M[Ge(OEt) 3](CO)nP5-n (9-11). Trimethylgermyl compounds M(GeMe3)(CO)nP5-n (12, 13) and the alkynylgermyl derivative Mn[Ge(CCPh)3](CO)3[PPh(OEt) 2]2 (14a) were also prepared by allowing trichlorogermyl compounds 1-4 to react with either MgBrMe or Li+CCPh-, respectively, in thf. Treatment of compound Re(GeCl3)(CO) 3[PPh(OEt)2]2 (4a) with SnCl 2•2H2O gave the stannyl-germyl derivative Re[GeCl2(SnCl3)](CO)3[PPh(OEt) 2]2 (15a). The complexes were characterised by spectroscopy and X-ray crystal structure determination of 4a, 5a, and 13a. © 2011 Elsevier B.V. All rights reserved.