14653-44-2Relevant articles and documents
Synthese von [(η5-C5H5)2Ti(Cl)(CCSiMe3)]Ni(CO) und dessen Reaktionverhalten gegenueber Phosphiten: die Festkoerperstruktur von (CO)2Ni[P(OC6H4CH3-2)3]2
Meichel, E.,Stein, Th.,Kralik, J.,Rheinwald, G.,Lang, H.
, p. 191 - 198 (2007/10/03)
Treatment of [Ti](Cl)(CCSiMe3) (1) {[Ti]=(η5-C5H5)2Ti} with Ni(CO)4 (2) in a 1:1 molar ratio produces the heterobimetallic early-late transition metal complex {[Ti](Cl)(CCSiMe3)}Ni(CO) (3), which features a low-valent Ni(CO) entity stabilized by a datively bonded Cl and a η2-coordinated Me3SiCC ligand. As side-products [Ti]Cl2 (8) and {[Ti](CCSiMe3)2}Ni(CO) (5) are formed. The latter complex can also be synthesized by the reaction of [Ti](CCSiMe3)2 (4) with equimolar amounts of 2. If 3 is reacted with stoichiometric amounts of P(OR)3 (6a, R=C6H5; 6b, R=C6H4CH3-2; 6c, R=C6H4t-Bu-2) the bis(alkynyl) titanocene 4, (CO)2Ni[P(OR)3]2 (7a, R=C6H5; 7b, R=C6H4CH3-2; 7c, R=C6H4t-Bu-2), complex 8, {[Ti](μ,η1:η2-CCSiMe3)}2 (9) along with Me3SiCC-CCSiMe3 (10) is produced. A possible mechanism for the formation of these species is presented. The solid-state structure of 7b is reported. Complex 7b crystallizes in the tetragonalic space group P-421c with the following parameters: a=14.852(2), b=14.852(2), c=19.410(4) Angstroem, V=4281.5(12) Angstroem3, Z=4 and ρ=1.271 g cm-3. Mononuclear 7b features a Ni(O) centre in a pseudo-tetrahedral environment, caused by the CO and P(OC6H4CH3-2)3 ligands.
Kinetics and mechanism of the reactions of di-μ-carbonyl-bis(cyclopentadienyl)dinickel(0) with monodentate ligands
Ellgen, Paul C.
, p. 232 - 239 (2008/10/08)
The ligands carbon monoxide, triphenylarsine, triphenyl phosphite, triphenylphosphine, ethyldiphenylphosphine, and tri-n-butylphosphine react with di-μ-carbonyl-bis(cyclopentadienyl)dinickel(0) to give nickelocene and diliganddicarbonylnickel(0) (eq 1). The kinetics of these reactions have been studied by following the carbonyl region infrared spectra of reaction mixtures or by manometric observation of carbon monoxide absorption. Complicated behavior is observed with tri-n-butylphosphine. The dependence on carbon monoxide concentration was not studied, but reaction according to (1) is much slower than the rate reported for carbon monoxide exchange. For the other ligands studied, a second-order rate law, first order in each reactant, is observed: -d[Ni2(CO)2(C5H5)2]/dt = k[Ni2(CO)2(C5H5)2][L]. The reaction mechanism is discussed. A complex mechanism can be shown to be quantitatively consistent with the data for the reaction with tri-n-butylphosphine.
