Abstract
A family of germyl rhodium complexes derived from the PGeP germylene 2,2’‐bis(di‐isopropylphosphanylmethyl)‐5,5’‐dimethyldipyrromethane‐1,1’‐diylgermanium(II), Ge(pyrmP i Pr2)2CMe2 (1), has been prepared. Germylene 1 reacted readily with [RhCl(PPh3)3] and [RhCl(cod)(PPh3)] (cod=1,5‐cyclooctadiene) to give, in both cases, the PGeP‐pincer chloridogermyl rhodium(I) derivative [Rh{κ3 P,Ge,P‐GeCl(pyrmP i Pr2)2CMe2}(PPh3)] (2). Similarly, the reaction of 1 with [RhCl(cod)(MeCN)] afforded [Rh{κ3 P,Ge,P‐GeCl(pyrmP i Pr2)2CMe2}(MeCN)] (3). The methoxidogermyl and methylgermyl rhodium(I) complexes [Rh{κ3 P,Ge,P‐GeR(pyrmP i Pr2)2CMe2}(PPh3)] (R=OMe, 4; Me, 5) were prepared by treating complex 2 with LiOMe and LiMe, respectively. Complex 5 readily reacted with CO to give the carbonyl rhodium(I) derivative [Rh{κ3 P,Ge,P‐GeR(pyrmP i Pr2)2CMe2}(CO)] (6), with HCl, HSnPh3 and Ph2S2 rendering the pentacoordinate methylgermyl rhodium(III) complexes [RhHX{κ3 P,Ge,P‐GeMe(pyrmP i Pr2)2CMe2}] (X=Cl, 7; SnPh3, 8) and [Rh(SPh)2{κ3 P,Ge,P‐GeMe(pyrmP i Pr2)2CMe2}] (9), respectively, and with H2 to give the hexacoordinate derivative [RhH2{κ3 P,Ge,P‐GeMe(pyrmP i Pr2)2CMe2}(PPh3)] (10). Complexes 3 and 5 are catalyst precursors for the hydroboration of styrene, 4‐vinyltoluene and 4‐vinylfluorobenzene with catecholborane under mild conditions.
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