113132-32-4Relevant academic research and scientific papers
A triad of electron-rich μ2-alkylidene complexes M2(CO)6[μ-CHC(Ph)NEt2](μ-PPh2) (M = Fe, Ru, Os) via the addition of diethylamine to the acetylides M2(CO)6(μ2-η2-C≡CPh) (μ-PPh2): Spectroscopic properties and structural chemistry
Cherkas, Andrew A.,Mott, Graham N.,Granby, Ruthanne,Maclaughlin, Shane A.,Yule, John E.,Taylor, Nicholas J.,Carty, Arthur J.
, p. 1115 - 1121 (2008/10/08)
The synthesis, X-ray structures, and IR and 1H, 13C, and 31P NMR spectroscopic characterization of a triad of zwitterionic μ-alkylidene compounds, M2(CO)6[μ-CHC(Ph)NEt2](μ-PPh2) (2a, M = Fe; 2b, M = Ru; 2c, M = Os), are described. Complex 2 is formed by addition of diethylamine to the β-carbon atom of the μ2-η2-acetylide of 1, M2(CO)6(μ2-η 2-C≡CPh)(μ-PPh2) (1a, M = Fe; 1b, M = Ru; 1c, M = Os), with hydrogen transfer across the acetylide triple bond. The 1H and 13C NMR chemical shifts for 2a-c indicate a very electron-rich M-C-M core. Crystals of 2a-c are monoclinic, space group P21/n, with unit cell dimensions: 2a, a = 14.694 (7) A?, b = 13.653 (7) A?, c = 17.787 (7) A?, β = 99.03 (7)°; 2b, a = 10.066 (1) A?, b = 20.297 (3) A?, c = 17.512 (2) A?, β = 105.90 (1)°; 2c, a = 14.767 (2) A?; b = 14.174 (2) A?, c = 17.922 (3) A?, β = 99.92 (1)°. The structures were solved and refined to the following R and Rw values: 2a, R = 0.035, Rw = 0.041, on 3760 observed (I ≥ 3σ(I)) data; 2b, R = 0.030, Rw = 0.037, on 3494 data; 2c, R = 0.043, Rw = 0.050, on 3064 data. The three molecules are isostructural with a metal-metal bond bridged by a phosphide group and an electron-rich μ-alkylidene group. Structural changes down the triad are discussed in the context of metal-alkylidene bonding.
