Reaction of ylides with cationic transition metal olefin and tetrahydrofuran complexes

Haloalkyl complexes of the transition metals. Part 3. Reactions of some chloromethyl and methoxymethyl complexes of molybdenum, tungsten, manganese, rhenium, iron, and ruthenium with some tertiary phosphine and related ligands

“…A mixture of two products, viz. (4) and (9), was isolated from the reaction of (1) with PMezPh (1 : 1 molar ratio of reactants) in acetonitrile for 17.5 h. If the reaction was carried out for a longer period (5 d) with an excess of PMezPh, then (9) was the only product isolated (81% crude yield) ; these results suggest that (4) is converted into (9). From the reactions of (1) with PMe3 or PEt,Ph were isolated (10) and ( 11) respectively as air-stable, yellow crystalline BPh4-salts.…”

Four-Coordinate Titanium Alkylidene Complexes: Synthesis, Reactivity, and Kinetic Studies Involving the Terminal Neopentylidene Functionality

“…Although the preparation of 3-Cl and 3-BH 4 is straightforward and involves simple anion exchange using MgCl 2 and LiBH 4 , the synthesis of 3-Br was somewhat less obvious. Greater yields of 3-Br were obtained when the LiBr-ylide adduct Ph 3 PCH 2 ·LiBr was used in place of MgBr 2 . The ylide salt adduct is apparently a much more soluble Br - source than MgBr 2 , and rapid Br - exchange reduces the decomposition of thermally unstable 3-Br (vide infra).…”

Nucleophilic Attack of Carbonyl-Stabilized Phosphorus Ylides on Neutral and Cationic Alkene Platinum(II) Complexes

“…Although phosphorus ylides have been shown to function as ligands with virtually every metal of the periodic table, their use as nucleophiles toward coordinated ligands has been scarcely examined. Thus, the complexes [Fe(η 5 -Cp)(CO)(L)(η 2 −CH 2 CH 2 ] (L = CO, PPh 3 ) react with Ph 3 PCHR (R = H, CO 2 Me, respectively) to give [Fe(η 5 -Cp)(CO)(L){CH 2 CH 2 CHR(PPh 3 )}]. Similarly, the cluster [FeCo 2 (CO) 9 (μ 3 -η 2 -CCH 2 )] reacts with Ph 3 PCHR (R = H, CO 2 Et, C(O)Ph, SiMe 3 ) to give [FeCo 2 (CO) 9 {μ 3 -CCH 2 CHR(PPh 3 )}] …”