Synthesis and Reactivity of Bromo-mer-tricarbonyl-trans-bis[tri(1-cyclo- hepta-2,4,6-trienyl)phosphane]-manganese, MnBr(CO)3[P(C7H7)3]2
نویسندگان
چکیده
The reaction of Mn(X)(CO)5 (X = Cl, Br, I) with 2 equivalents of tri(1-cyclohepta-2,4,6trienyl)phosphane, P(C7H7)3 ((1); [P] if coordinated to a metal) led stepwise first to cis{Mn(X)(CO)4[P]} (X = Cl (4a), Br (4b), I (4c)) and then to mer,trans-{Mn(X)(CO)3[P]2} (X = Cl (5a), Br (5b), I (5c)). Nucleophilic displacement of the bromo ligand from (5b) by one-, threeor five-electron ligands gave the pseudohalide complexes mer,trans-{Mn(X)(CO)3[P]2} (X = NCO (5d) and NCS (5e)), the acetylacetonate derivative Mn(acac)(CO)2[P]2 (6) and the halfsandwich complexes CpMn(CO)2[P] (7) or TpMn(CO)3 (8). According to the X-ray structure determination of 5e the thiocyanate ligand is N-coordinated.
منابع مشابه
Dinuclear Derivatives of Mn2(CO)10 with the Ligand Tri(1-cyclohepta- 2,4,6-trienyl)phosphane, P(C7H7)3, and their Oxidative Cleavage
The photo-induced reaction of Mn2(CO)10 with the olefinic phosphane P(C7H7)3 (1; [P] if coordinated to a metal) leads stepwise to the axially substituted derivatives ax-{Mn2(CO)9[P]} (2) and ax,ax-{Mn2(CO)8[P]2} (3). Oxidative cleavage of 3 by halogens gives cis-{Mn(X)(CO)4[P]} (X = Cl (4a), Br (4b), I (4c)), whereas oxidation of 3 with NOBF4 provides a route to the salt {Mn(CO)4[P]}BF4 (5) whi...
متن کاملMolecular Structure and Reactivity of Tri(1-cyclohepta-2,4,6-trienyl)amine, N(C7H7)3
Compared with the tertiary phosphane P(C7H7)3 (1), the amine N(C7H7)3 (2) possesses the structure of a flattened trigonal pyramid with a sum of CNC angles of 350.0◦ (cf. 300.2◦ (av.) in 1). The heteroatom (with the lone pair) is situated 27.0 pm above the C3 basal plane in 2, but 86.4 pm in 1. The amines N(C7H7)3 (2), NH(C7H7)2 (2a) and N(Ph)(C7H7)2 (2b) react with tropylium tetrafluoroborate, ...
متن کاملOligonuclear Tricarbonylchromium- and Tricarbonyltungsten Derivatives of Tris(l-cyclohepta-2,4,6-trienyl)phosphane, P(C7H7)3 , and Related Ligands
Z. Naturforsch. 54 b, 63-72 (1999); received August 3, 1998 Halfsandwich Compounds, Cycloheptatrienyl Complexes, Chromium, Tungsten, X-Ray Data A series of trinuclear carbonylmetal complexes of tri(l-cyclohepta-2,4,6-trienyl)phosphane, P(C? 1̂ 7)3 (1), has been prepared by the reaction of P(SiMe3)3 with ^-tropylium halfsand wich salts, [(7/7-C7H7)M(CO)3]BF4, (M = Cr, Mo, W). While phosphorus re...
متن کاملPlatinum(II) and Palladium(II) Dichalcogenolene Complexes Containing the Ligand Tri(1-cyclohepta-2,4,6-trienyl)phosphane. Molecular Structure, Intramolecular Dynamics in Solution, and the Absolute Signs of Coupling Constants
Tri(1-cyclohepta-2,4,6-trienyl)phosphane, P(C7H7)3 (1), serves as a bidentate chelating ligand [P] in platinum(II) and palladium(II) complexes. Here the synthesis of the four dichalcogenolene complexes [P]M[E2C2(CO2Me)2] (4) (M = Pt) and 5 (M = Pd) with E = S (a) and Se (b) from the reaction of the respective dicyclopentadienyltitanium dichalcogenolenes, Cp2Ti[E2C2(CO2Me)2], and [P]MCl2 with M ...
متن کاملphosphane, P(C7H7)3, as a Tripodal Tetradentate Ligand in Cationic, Five-coordinate Complexes of Platinum(II) and Palladium(II)
Chloride abstraction, using AgPF6, from tri(1cyclohepta-2,4,6-trienyl)phosphane platinum and palladium dichloride, [P]MCl2 [M = Pt (1), Pd (2)], affords the complexes {[P]MCl}PF6 [M = Pt (3), Pd (4)] in good yields. The central metal is coordinated by the chloro ligand, the phosphorus atom and by three η2-C=C units, one of each C7H7 ring. This assignment of a highly symmetrical C3v structure is...
متن کامل