SYNTHESES AND SOLID-STATE STRUCTURES OF [HB(3,5-ME(2)PZ)(3)]INFE(CO)(4) AND [HB(3,5-ME(2)PZ)(3)]INW(CO)(5) (PZ=PYRAZOLYL RING) - INTERMETALLIC COMPLEXES WITH SHORT METAL-METAL BONDS

The reaction of [HB(3,5-Me(2)pz)(3)]InCl2.THF (pz = pyrazolyl ring) with Na2Fe(CO)(4) in THF yields [HB(3,5-Me(2)pz)(3)]InFe(CO)(4). The solid state structure shows that the geometry about the iron atom is a trigonal bipyramid with the indium located at an axial position. The In-Fe bond length of 2.463(2) Angstrom is the shortest reported to date. Molecular orbital calculations indicate that little charge polarization exists in the iron-indium bond. The reaction of [HB(3,5-Me(2)pz)(3)]InCl2. THF with Na2W(CO)(5)S in THF yields [HB(3,5-Me(2)pz)(3)]InW-(CO)(5). This complex, with an In-W bond distance of 2.783(2) Pi, is the first complex with an In-W bond to be structurally characterized. Crystal data: [HB(3,5-Me(2)pz)(3)]InFe-(CO)(4).1.5C(6)H(6), monoclinic, P2(1)/n, a = 13.927(2), b = 13.701(2), and c = 17.957(3) Angstrom, beta = 97.97(1)degrees, V = 3393.3(9) Angstrom(3), Z = 4, T = 296 K, R = 6.84%; [HB(3,5-Me(2)pz)3]InW(CO)(5), monoclinic, C2/c, a = 13.609(4), b = 19.478(9), and c = 20.099(9) Angstrom, beta = 107.63(4)degrees, V = 5077(7) Angstrom(3), Z = 8, T = 296 K, R = 6.46%.