Silica-grafted 16-electron hydride pincer complexes of iridium(III) and their soluble analogues: synthesis and reactivity with CO.

The dihydride complexes [IrH2(POCOP)] (1a) and [IrH2(PCP)] (1b) (POCOP = 1,3-bis((di-tert-butylphosphino)oxy)benzene; PCP = 1,3-bis((di-tert-butylphosphino)methyl)benzene) react with the surface silanols of mesoporous amorphous silica (SBA-15) to give H2 and the silica-grafted, 16-electron iridium(III) monohydride species [IrH(O-SBA-15)(pincer)] (2a and 2b). These materials contain a single iridium(III) species, that is a highly dispersed, coordinatively unsaturated siloxo hydride complex, as indicated by solid-state spectroscopic data. The siloxo complexes [IrH((i)Bu-POSS)(POCOP)] (3a) and [IrH((i)Bu-POSS)(PCP)] (3b) ((i)Bu-POSS = OSi8O12(i)Bu7) were prepared as soluble analogues of 2a and 2b to support their spectroscopic characterization. The coordinatively unsaturated, 16-electron species 2a and 2b react with CO to give the six-coordinate iridium(III) adducts [IrH(O-SBA-15)(CO)(POCOP)] (7a) and [IrH(O-SBA-15)(CO)(PCP)] (7b). Due to dissimilar electronic properties of the pincer ligands, 7a undergoes reductive elimination of the silanol forming the Ir(I) complex [Ir(CO)(POCOP)] (8a), whereas 7b is stable in oxidation state of III. The homogeneous siloxo carbonyl complexes [IrH((i)Bu-POSS)(CO)(POCOP)] (9a), [IrH((i)Bu-POSS)(CO)(PCP)] (9b), and [IrH(OSiMe3)(CO)(POCOP)] (11a) were prepared to substantiate the reactivity and the characterization of the silica grafted species.