TY - JOUR
T1 - Crystal and molecular structure of (η3-allyl)carbonylchlorobis(dimethylphenylphosphine)- iridium(III) hexafluorophosphate, [Ir(η3-C3H5)Cl(CO)(P(CH3)2(C6H5))2][PF6
AU - Kaduk, James A.
AU - Poulos, Arthur T.
AU - Ibers, James A.
N1 - Funding Information:
his encouragement and helpful discussions. J.A.K. wishes to acknowledge the support of an NSF predoctoral fellowship_ This work was supported by the National Science Foundation.
PY - 1977/3/1
Y1 - 1977/3/1
N2 - The structure of (η3-allyl)carbonylchlorobis(dimethylphenylphosphine)-iridium(III) hexafluorophosphate, [Ir(η3-C3H5)Cl(CO)(P(CH3)2(C6H5))2][PF6], has been determined from three-dimensional X-ray data to add support for a proposed mechanism of the oxidative addition of allyl halides to IrX(CO)(PR3)2 (X = halide). The compound crystallizes in space group C52h-P21/c with four formula units in a cell of dimensions a = 11.027(1), b = 12.230(2), c = 19.447(5) Å, and β = 103.16(2)0. Least-squares refinement of the structure has led to a value of the conventional R index (on F) of 0.066 for the 3018 independent reflections having F20>3-(F20). The crystal structure consists of discrete, monomericions. The hexafluorophosphate anion is disordered. The coordination geometry around the iridium atom may be described as octahedral, with the chloro ligand trans to the carbonyl group and each phosphorus atom trans to a terminal carbon of the allyl group. Structural parameters: Ir-P = 2.366(4), 2.347(3);Ir-Cl = 2.389(3); Ir-C(allyl) = 2.28(1), 2.24(1),2.25(1); Ir-C (carbonyl) = 1.85(1) Å; P-Ir-P = 105.7(1); C(terminal)-Ir-C(terminal) = 66.2(8); C-C-C = 125(2)o. The allyl group makes an angle of 126o with the P-Ir-P plane. Correlations between geometric structure and number of d electrons are noted among several M-C3H5-complexes, and are interpreted in the light of theoretical models of the M-C3H5- bond.
AB - The structure of (η3-allyl)carbonylchlorobis(dimethylphenylphosphine)-iridium(III) hexafluorophosphate, [Ir(η3-C3H5)Cl(CO)(P(CH3)2(C6H5))2][PF6], has been determined from three-dimensional X-ray data to add support for a proposed mechanism of the oxidative addition of allyl halides to IrX(CO)(PR3)2 (X = halide). The compound crystallizes in space group C52h-P21/c with four formula units in a cell of dimensions a = 11.027(1), b = 12.230(2), c = 19.447(5) Å, and β = 103.16(2)0. Least-squares refinement of the structure has led to a value of the conventional R index (on F) of 0.066 for the 3018 independent reflections having F20>3-(F20). The crystal structure consists of discrete, monomericions. The hexafluorophosphate anion is disordered. The coordination geometry around the iridium atom may be described as octahedral, with the chloro ligand trans to the carbonyl group and each phosphorus atom trans to a terminal carbon of the allyl group. Structural parameters: Ir-P = 2.366(4), 2.347(3);Ir-Cl = 2.389(3); Ir-C(allyl) = 2.28(1), 2.24(1),2.25(1); Ir-C (carbonyl) = 1.85(1) Å; P-Ir-P = 105.7(1); C(terminal)-Ir-C(terminal) = 66.2(8); C-C-C = 125(2)o. The allyl group makes an angle of 126o with the P-Ir-P plane. Correlations between geometric structure and number of d electrons are noted among several M-C3H5-complexes, and are interpreted in the light of theoretical models of the M-C3H5- bond.
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U2 - 10.1016/S0022-328X(00)89715-6
DO - 10.1016/S0022-328X(00)89715-6
M3 - Article
AN - SCOPUS:27644494626
SN - 0022-328X
VL - 127
SP - 245
EP - 260
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 2
ER -