CARBONYLATION OF IRIDIUM(I) AND IRIDIUM(III) COMPLEXES, TRANS-IR(CO)(R)(P(P-TOLYL)(3))(2) (R=ME, OME, OCH(2)PH, OC(6)H(4)ME, OH) AND IR(CO)(ME) (SO4)(P(P-TOLYL)(3))(2), AND FACILE ELIMINATION OF HARD LIGANDS -CRYSTAL AND MOLECULAR-STRUCTURES OF IR(CO)(ME)(SO4)(P(P-TOLYL)(3))(2)AND [IR(CO)(3)(P(P-TOLYL)(3))(2)][HSO4]
Sl. Randall et al., CARBONYLATION OF IRIDIUM(I) AND IRIDIUM(III) COMPLEXES, TRANS-IR(CO)(R)(P(P-TOLYL)(3))(2) (R=ME, OME, OCH(2)PH, OC(6)H(4)ME, OH) AND IR(CO)(ME) (SO4)(P(P-TOLYL)(3))(2), AND FACILE ELIMINATION OF HARD LIGANDS -CRYSTAL AND MOLECULAR-STRUCTURES OF IR(CO)(ME)(SO4)(P(P-TOLYL)(3))(2)AND [IR(CO)(3)(P(P-TOLYL)(3))(2)][HSO4], Organometallics, 13(12), 1994, pp. 5088-5095
Carbonylation of several iridium(I) complexes, trans-Ir(CO)(R)(P(p-tol
yl)(3))(2) lead to products Ir(Co)(2)(C(O)R)(P(p-tolyl)(3))(2), R = Me
, OCH(2)Ph; and Ir-2(CO)(6)(P(p-tolyl)(3))(2), R = OH, OMe, and OC(6)H
(4)Me) that depend on the nature of the R group. Carbonylation of the
iridium(III) complex, Ir(CO)(Me)(SO4)(P(p -tolyl)(3))(2) leads to two
iridium products, [Ir(CO)(3)(P(p-tolyl)(3))(2)(+)] and Ir(CO)(3)(C(O)M
e)(P(p-tolyl)(3))(2) by two different pathways. Structures of Ir(CO)(M
e)(SO4)- (P(p-tolyl)(3))(2) and [Ir(CO)(3)(P(p-tolyl)(3))(2)][HSO4] we
re determined to assist in the interpretation. The complex Ir(CO)(Me)(
SO4)(P(p-tolyl)(3))(2) crystallizes in the orthorhombic space group Pb
cn with a = 18.237(3), b = 12.572(2), c = 18.584(2) Angstrom, V = 4260
.9(11) Angstrom(3) and Z = 4. The structure was refined to R = 1.98% f
or 1640 reflections with F > 6 sigma(F). The molecule lies on a site o
f Ct symmetry, necessitating a disorder of carbonyl and methyl ligands
. Bond distances around the octahedral iridium(III) center include Ir-
CO = 1.823(13), Ir-CH3 = 2.127(14), Ir-P = 2.398(1) and Ir-O(SO4)= 2.1
19(4) Angstrom. The species [Ir(CO)(3)(P(p-tolyl)(3))(2)][HSO4] crysta
llizes in the monoclinic space group P2(1)/n with a = 11.490(2), b = 1
2.255(3), c = 30.873(7) Angstrom, beta = 92.826(17)degrees, V = 4342.0
(15) Angstrom(3) and Z = 4. The structure was refined to R = 6.09% for
2591 reflections with F > 6 sigma(F). The Ir(CO)(3)P-2 core of the ca
tion has a geometry slightly distorted from D-3h symmetry, with Ir-P =
2.363(5) and 2.374(5) Angstrom and Ir-CO = 1.921(21)-2.012(28) Angstr
om. The HSO4- anion undergoes substantial librational motion (or is di
sordered) and is associated with S-O distances ranging from 1.31(4) th
rough 1.49(3) Angstrom.