Variable Coordination Modes in Dialkyldithiophosphinato Complexes of Group 13 Metals:  The X-ray Single Crystal Structures of Tris(diisobutyldithiophosphinato)gallium(III) and -indium(III)

Abstract

The new compounds [In(S2PiBu2)3] (1) and [Ga(S2PiBu2)3] (2) have been synthesized and characterized. Whereas in the structure of compound 1 the metal center was found to be six-coordinate, the metal center in compound 2 is four-coordinate, being bound to only one chelating and two pendant diisobutyldithiophsophinate ligands in a distorted tetrahedral geometry.

Gallium and indium dithiocarboxylates: Synthesis, spectroscopic characterization and structure of [MeGa(S2Ctol)2]

“…The two shorter Ga-S distances in each molecule are comparable (av. 2.317 Å ) and are well within the single Ga-S bond [14,30]. However, this distance is smaller than the one reported for [[Ga{S 2 CN(CH 2 CH 2 ) 2 O} 3 ] (av.…”

“…Thus a variety of gallium and indium complexes with thiolates [6], pyridine-2-thiolate [7], monothiocarboxylate [8], and dithiolates (xanthates [9][10][11], dithiocarbamates [12,13], diorganodithio-phosphinate/-phosphates [14][15][16][17]) have been synthesized and characterized. Organogallium and indium thiolates, [R 2 MSR 0 ] 2 and [RM(SR 0 ) 2 ] 2 , are often isolated as dimers.…”

Gallium(III) and indium(III) dithiolate complexes: Versatile precursors for metal sulfides

“…12,18,[21][22][23]25,30,31,33,38,39,47,49,[52][53][54][55][56][57][58][59][60][61][62][63][64][65][66][67] The complexes are discrete monomers and in general have distorted geometries owing to the restricted bite of the dithio ligands. The S-M-S angle of the chelating dithio ligands varies between 66⋅6 and 81⋅7°, the Scheme 1.…”

“…The tris complexes of gallium and indium are isostructural in nature and have a six coordinate metal atom with the exception of [Ga(S 2 PBu i 2 ) 3 ] which has a distorted tetrahedral geometry around gallium (figure 1). 25 The geometries of tris complexes can be trigonal prismatic or distorted octahedral (scheme 2). In dithiocarbamate complexes, the C-N distances are significantly shorter than the single N-C bond, due to delocalization of pπ electrons of C=S linkage in .…”

Gallium: Inorganic ChemistryBased in part on the article Gallium: Inorganic Chemistry by Andrew R. Barron which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

“…150 The related indium compounds [In(S 2 PR) 3 ] (R = Me, Et, OEt, Ph) are monomeric in the solid state in contrast to the dinuclear species seen for the related group 12 zinc and cadmium species. 3 .…”