Unusual Hydrolysis Reactions of cis-Bis((2,2‘-biphenylylene)phosphochloridite ester)tetracarbonylmolybdenum(0)

Abstract

The hydrolysis of cis-Mo(CO) 4 (2,2′-C 12 H 8 O 2 PCl) 2 (1) in the presence of excess triethylamine and water yields [ 3) and free triethylamine in solution. The hydrolysis of 1 with a stoichiometric amount of triethylamine and water yields only 3. A Scatchard plot for the reaction of 3 and triethylamine to form 2 at 25 °C gives an equilibrium constant of 5.8 × 10 -3 for the reaction. Fitting the variabletemperature 31 P{ 1 H} NMR spectra of a CD 2 Cl 2 solution of 3 and 0.5 equiv of triethylamine using the gNMR program gives an activation energy of 47.4 kJ/mol for the reaction. The diastereomers of 3 crystallize with very different morphologies, allowing the X-ray crystal structures of both enantiomers to be determined. The 3R*R* diastereomer crystallizes in the noncentrosymmetric P2 1 2 1 2 1 space group, but the 3R*S* diastereomer crystallizes in the centrosymmetric P2 1 /c space group. The most interesting feature of the structures of 3R*R* and 3R*S* is the strong, intramolecular hydrogen bonding between the 2,2′-C 12 H 8 O 2 -POH and 2,2′-C 12 H 8 O 2 POligands that result in short O-O distances in both enantiomers (2.520(6) Å in 3R*R* and 2.373(11) Å in 3R*S*). The hydrogen bonding in both diastereomers is asymmetric, in contrast to previous speculation in the literature.

Synthesis, linear and nonlinear optical properties of phosphonato-substituted bithiophenes derived from 2,2′-biphenol

“…Both 10O and 10Se adopt a twist boat conformation similar to that in coordinated (2,2′-biphenylene)phosphites. [55][56][57] In this conformation, O1 is the bow, C12 and C7 are the stern and P, O2, C1 and C6 form the base with the P-O2 and C1-C6 bonds crossing the least-squares plane defined by these four atoms in different directions resulting in…”