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 Pr ) CMe (1), has been prepared. Germylene 1 reacted readily with [RhCl(PPh ) ] and [RhCl(cod)(PPh )] (cod=1,5-cyclooctadiene) to give, in both cases, the PGeP-pincer chloridogermyl rhodium(I) derivative [Rh{κ P,Ge,P-GeCl(pyrmP Pr ) CMe }(PPh )] (2). Similarly, the reaction of 1 with [RhCl(cod)(MeCN)] afforded [Rh{κ P,Ge,P-GeCl(pyrmP Pr ) CMe }(MeCN)] (3). The methoxidogermyl and methylgermyl rhodium(I) complexes [Rh{κ P,Ge,P-GeR(pyrmP Pr ) CMe }(PPh )] (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{κ P,Ge,P-GeR(pyrmP Pr ) CMe }(CO)] (6), with HCl, HSnPh and Ph S rendering the pentacoordinate methylgermyl rhodium(III) complexes [RhHX{κ P,Ge,P-GeMe(pyrmP Pr ) CMe }] (X=Cl, 7; SnPh , 8) and [Rh(SPh) {κ P,Ge,P-GeMe(pyrmP Pr ) CMe }] (9), respectively, and with H to give the hexacoordinate derivative [RhH {κ P,Ge,P-GeMe(pyrmP Pr ) CMe }(PPh )] (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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