TY - JOUR
T1 - A Comparative Study of Isostructural Palladium and Platinum Methyl Complexes. The Structures of cis-Dimethylbis(diphenylmethylphosphine)palladium(II) and cis-Dlmethylbis(diphenylmethylphosphine)platlnum(II)
AU - Wisner, Jean M.
AU - Bartczak, Tadeusz J.
AU - Ibers, James A.
PY - 1986/1/1
Y1 - 1986/1/1
N2 - The structures of cis-dimethylbis(diphenylmethylphosphine)palIadium(II) and cis-dimethylbis(di-phenylmethylphosphine)platinum(II) have been determined crystallographically at -162 °C. The palladium complex crystallizes from acetone in the monoclinic space group with four formula units in a unit cell of dimensions a =8.882 (3) A, b = 26.500 (7) A, c = 11.168 (4) A, and ß= 108.27 (4)°. The structure has been refined to an R index on F2of 0.038 for 4799 observations and 280 variables. The platinum congener crystallizes from a benzene/ethanol mixture with four molecules in the space group of the monoclinic system in a cell of dimensions a =8.859 (4) A, b = 26.302 (10) A, c = 11.215 (5) A, and ß = 108.60 (2)°. The Pt structure has been refined to an R index on F2 of 0.078 for 7678 observations and 280 variables. Both complexes possess slightly distorted square-planar geometry: P(l)-Pd-P(2) = 98.24 (4)°, P(l)-Pt-P(2) = 97.75 (6)°, C(l)-Pd-C(2) = 82.9 (1)°, and C(l)-Pt-C(2) = 81.9 (2)°. Some important bond distances are as follows: Pd-C = 2.089 (3), 2.090 (3) A; Pt-C = 2.122 (6), 2.119 (5) A; Pd-P = 2.326 (1), 2.321 (1) A; Pt-P = 2.285 (2), 2.284 (2) A. Comparison of the two structures shows a lengthening of the M-C bonds and a concomitant shortening of the M-P bonds when the central metal is changed from palladium to platinum. These structural data are correlated with differences in reactivity. In addition, sets of isostructural compounds in other metal triads are surveyed for analogous trends in bond distances.
AB - The structures of cis-dimethylbis(diphenylmethylphosphine)palIadium(II) and cis-dimethylbis(di-phenylmethylphosphine)platinum(II) have been determined crystallographically at -162 °C. The palladium complex crystallizes from acetone in the monoclinic space group with four formula units in a unit cell of dimensions a =8.882 (3) A, b = 26.500 (7) A, c = 11.168 (4) A, and ß= 108.27 (4)°. The structure has been refined to an R index on F2of 0.038 for 4799 observations and 280 variables. The platinum congener crystallizes from a benzene/ethanol mixture with four molecules in the space group of the monoclinic system in a cell of dimensions a =8.859 (4) A, b = 26.302 (10) A, c = 11.215 (5) A, and ß = 108.60 (2)°. The Pt structure has been refined to an R index on F2 of 0.078 for 7678 observations and 280 variables. Both complexes possess slightly distorted square-planar geometry: P(l)-Pd-P(2) = 98.24 (4)°, P(l)-Pt-P(2) = 97.75 (6)°, C(l)-Pd-C(2) = 82.9 (1)°, and C(l)-Pt-C(2) = 81.9 (2)°. Some important bond distances are as follows: Pd-C = 2.089 (3), 2.090 (3) A; Pt-C = 2.122 (6), 2.119 (5) A; Pd-P = 2.326 (1), 2.321 (1) A; Pt-P = 2.285 (2), 2.284 (2) A. Comparison of the two structures shows a lengthening of the M-C bonds and a concomitant shortening of the M-P bonds when the central metal is changed from palladium to platinum. These structural data are correlated with differences in reactivity. In addition, sets of isostructural compounds in other metal triads are surveyed for analogous trends in bond distances.
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U2 - 10.1021/om00141a018
DO - 10.1021/om00141a018
M3 - Article
AN - SCOPUS:0011502290
SN - 0276-7333
VL - 5
SP - 2044
EP - 2050
JO - Organometallics
JF - Organometallics
IS - 10
ER -