Abstract
The reaction of the dichlorogermane Me~2~GeCl~2~ and stannanes R~2~SnCl~2~ (R = Me, Bu) with the alkali tungsten salts M[(η^5^‐C~5~R′~5~)L(OC)~2~W] (L = CO, PPh~3~; M = Li, Na; R′ = H, Me) yields via alkali salt elimination a range of novel chlorostannyl‐ and chlorogermyl‐functionalized tungsten complexes of the general formula [(η^5^‐C~5~R′~5~)L(OC)~2~W(ER~2~Cl)] (R′ = H, Me; L = CO, PPh~3~; E = Ge, Sn; R = Me, Bu) (3a–e). The use of the phosphane‐substituted tungsten anion Na[(η^5^‐C~5~Me~5~)(Ph~3~P)(OC)~2~W] (1c) and Me~2~SnCl~2~ leads to a mixture consisting of the mono‐ (3e) as well as the di‐substituted stannyl compound [{(η^5^‐C~5~H~5~)(Ph~3~P)(OC)~2~W}~2~(SnMe~2~)] (4). Access to 3a is also given by reaction of ClMe~2~Sn–C~5~H~5~ (5) with [(MeCN)~3~W(CO)~3~] which includes chemoselective tin shift from the cyclopentadiene to the tungsten atom. In addition, a successive chlorination of [(η^5^‐C~5~H~5~)(OC)~3~W(SnMe~3~)] (6) via [(η^5^‐C~5~H~5~)(OC)~3~W(SnMe~2~Cl)] (3a) and [(η^5^‐C~5~H~5~)(OC)~3~W(SnMeCl~2~)] (7) to [(η^5^‐C~5~H~5~)(OC)~3~W(SnCl~3~)] (8) is presented. All new compounds have been fully characterized by elemental analyses and in solution by IR and multinuclear NMR spectroscopy. The crystal structures of complexes 3b–d and 8 were presented and discussed, showing bond lengths of 2.6272(4) Å for Ge–W, 2.7959(5) (3b), 2.7866(3) (3d) and 2.7244(3) (8) Å for the Sn–W bonds.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)