67010-37-1Relevant academic research and scientific papers
Solid State Structure of cis-[W(CO)4(pip)(PPh3)]
Harkreader, Jennifer L.,Frost, Brian J.
, p. 125 - 129 (2019)
The solid state structure of cis-[W(CO)4(PPh3)(pip)] (1) was determined by X-ray crystallography. cis-[W(CO)4(PPh3)(pip)] was synthesized by reaction of PPh3 with cis-[W(CO)4(pip)2] and isolated as yellow crystals. Compound 1 crystalized in the monoclinic space group P21/c and was found to have a distorted octahedral geometry. The P–W–N angle was slightly more acute than expected, presumably due to an unusual N–H?π interaction. Graphical Abstract: The solid state structure of cis-[W(CO)4(PPh3)(pip)] (1) is described with an P–W–N angle slightly more acute than expected, presumably due to an N–H?π interaction. [Figure not available: see fulltext.].
Volumes of Activation for Kinetically Labile Organometallic Complexes: Solvent Displacement from cis- in Chlorobenzene Solution
Awad, Hani H.,Dobson, Gerard R.,Eldik, Rudi van
, p. 1839 - 1841 (2007/10/02)
Large, positive, and similar volumes of activation, indicative of dissociative desolvation mechanisms, have been observed for chlorobenzene displacement by pyridine and through chelate ring closure, respectively, from cis- complexes
Time-Resolved IR Characterization of cis- and trans- in n-Heptane Solution: The Solvent as a Token Ligand in Short-Lived Reaction Intermediates
Dobson, Gerard R.,Hodges, P. Michael,Healy, Michael A.,Poliakoff, Martyn,Turner, James J.,et al.
, p. 4218 - 4224 (2007/10/02)
Time-resolved IR spectroscopy is used to identify the cis (6) and trans (5) isomers of (L = PPh3, P(O-i-Pr)3 and P(OEt)3, (s) = solvent) as the major primary photoproducts of the photolysis of LW(CO)5 (2) and cis-(pip)LW(CO)4 (3) (pip = piperidine) in n-heptane solution at room temperature.Matrix isolation experiments in solid Ar at 20 K with (PPh3)W(CO)5 help with the interpretation of these time-resolved spectra.In heptane solution, for each L, the cis isomer (6) is shorter lived than the trans (5), and there is no evidence for thermal interconversion of the two isomers, which react with CO at different rates.Intermediates with bulky ligands react with CO faster than those with sterically less demanding ligands.For all L, both isomers react with CO faster than does (4), the intermediate generated by flash photolysis of W(CO)6 under similar conditions.All of these formally unsaturated species appear to be solvated even in n-heptane solution, to give pseudooctahedral quasicoordination compounds .The term Token Ligand is proposed to signify this specific interaction of a solvent molecule with an otherwise vacant coordination site in reaction intermediates.
