Iron complexes phosphines

Many P(CH3)3 complexes of the first-row transition metals may be conveniently prepared by direct reaction with the appropriate anhydrous chromium (II), (III),3 cobalt(II),4 iron(II)s or hydrated iron(II),s nickel(II)4a>6,7 salt. The compound [(CH3)3P] 2FeCl2 is the starting material for a variety of phosphine iron complexes.4,8,9... 

Fig. 12.2 (a) Line drawing of an acetyl(carbonyl)(cyclopentadienyl)(phosphine)iron complex, (b) Stereoview of the same molecule. [From Korp, J. D. Bernal, I. J. Organomet. Chem. 1981, 220, 355-364. Reproduced with permission.)... 

More recently, Weber realized the synthesis of an iron complex of diphosphirane by reaction of the phosphine iron complex ([Fe]—PH2) with P-chlorophosphaalkene (Equation (14)). It was converted into the iron chromium complex, whose structure was elucidated by x-ray analysis <92CB1553>. 

As already mentioned earlier, the ruthenium complex [Ru(bdmpza) Cl(PPh3)2l (24) easily releases one of the two phosphine ligands and allows the substitution not only of a chlorido but also of a triphenylphosphine ligand for K -coordinating carboxylato or 2-oxocarboxylato ligands (58). The purpose of these studies was to find structural ruthenium models for the active site of 2-OG dependent iron enzymes, since ruthenium(II) complexes are low spin and thus suitable for NMR characterization, whereas ferrous iron complexes with NJV,0-ligands are often difficult to investigate, due to their... 

When L = phosphine the complex is stable to water and, in all cases, iron-silicon complexes are inert to methanol. 

CsHuN, Ethanamine, A-ethyl-A-methyl-tungsten complex, 26 40, 42 C6HF5, Benzene, pentafluoro-gold complexes, 26 86-90 C H4I2, Benzene, 1,2-diido-iridium complex, 26 125 CJT, Phenyl platinum complex, 26 136 C,H,N, Pyridine osmium complex, 26 291 OHtS, Benzenethiol osmium complex, 26 304 QH7P, Phosphine, phenyl-cobalt-iron complex, 26 353 QH 1-Butyne, 3,3-dimethyl-mercury-molybdenum-ruthenium complex, 26 329-335 C6H 4P, Phosphine, triethyl-platinum complex, 26 126 platinum complexes, 26 135-140 CsHisPO, Triethyl phosphite iron complex, 26 61... 

C2H,N, Pyridine, 3,5-dimethyl-palladium complex, 26 210 CbHsNO, Benzoyl isocyanide chromium com-C HbO, Ethanone, 1-phenyl-manganese complex, 26 156-158 CBH, 02, Methyl benzoate chromium complex, 26 32 C H i, o-Xylylene magnesium complex, 26 147 ChH P, Phosphine, dimethylphenyl-iron complex, 26 61 ruthenium complex, 26 273 ChH12, 1,5-Cyclooctadiene iridium complex, 26 122 ruthenium complexes, 26 69-72, 253-256 ChH OjPS, 2-Butenedioic acid, 2-(dimethylphosphinothioyl)-dimethyl ester, manganese complex, 26 163... 

CkH.jP, Phosphine, dimethylphenyl-ruthenium complex 26 273 C HU, Cyclooctene platinum complex, 26 139 C,H,N, Benzene, 2-isocyano-1,3-dimethyl-iron complexes, 26 53, 57 C H N, Benzenemethanamine, N,N,2-trimethyl-... 

C1bHi5As, Arsine, triphenyl-iron complex, 26 61 C H 5OjP, Triphenyl phosphite ruthenium complex, 26 178 CuHijP, Phosphine, triphenyl-cobalt complex, 26 190—197 cobalt-gold-ruthenium, 26 327 gold complex, 26 90, 325, 326 gold-manganese complex, 26 229 iridium complexes, 26 117-120, 122-125, 201, 202... 

C18H18, Benzene, l,3-butadiene-l,4-diyl-bis-cobalt complex, 26 195 C,8H33P, Phosphine, tricyclohexyl iron complex, 26 61 nickel complexes, 26 205, 206 C H 7OP, Benzenemethanol, 2-(diphenyl-phosphino)-... 

PChH , Phosphine, dimethylphenyl-iron complex, 26 61 PC, Hn, Phosphine, diphenyl-manganese complex, 26 158, 226-230 ruthenium complex, 26 264 PC 3H27, Phosphine, tributyl-iron complex, 26 61 PC,H , Phosphine, methyldiphenyl-iron complex, 26 61 PC, H Phosphine, triphenyl-cobalt complex, 26 190-197 cobalt-gold-ruthenium, 26 327... 

The iron compound readily sublimes and yields well-formed, black lustrous crystals. The cobalt complex will also readily sublime, but dependent upon the temperature at which the crystals are formed, they can be either black or brown in color. The crystal structures of both the cobalt and iron complexes have been determined.3 The nickel complex sublimes only in small amounts with difficulty. All three complexes are unstable to air and water, and the nickel complex readily undergoes thermal decomposition above 100°C. All three compounds will also readily form complexes with a variety of donor ligands such as tertiary arsines or phosphines. The nickel compound usually forms 2 1 adducts such as [(C6HS )3P]2Ni(NO)I, while the iron and cobalt complexes often undergo disproportionation.5... 

Ohst and Kochi (1986) traced changes in the electron structure that take place during substitution of the triethyl phosphine ligand for the carbonyl ligand in the iron-phenyl-phosphine-carbonyl complex see Scheme 1-50. 

The initial anion-radical of Scheme 1-50 is formed from the diamagnetic ternary nuclear complex upon one-electron reduction. This anion radical undergoes spontaneous breaking of one of the phosphine-iron bonds. The further substitution restores the Fe-P bond, which has been opened previously. Such restoration makes the whole reaction macroscopically reversible (in the sense of the cluster-skeleton preservation). 

Chatancin, via ring-closing metathesis, 11, 252 Chelate coordination, monoenes, in Pd(II) complexes, 8, 331 Chelated alkenes, with iron, 6, 133 Chelated allyl complexes, with iron, 6, 140 Chelating aryloxides, with Zr(IV), 4, 784 Chelating bis(amido) complexes, with Zr(IV), 4, 767 Chelating bis(amido) phosphine-donor complexes, with Zr(IV), 4, 816... 

Reactions of complexes of 1,2-cycloheptadienes have received only cursory attention. 1,2-cycloheptadiene is readily displaced from bisftriphenyl-phosphine)platinum(O)118 [Eq. (54)], but no reagent has been found that will displace the allene from iron.119 Reaction of the iron complex with alcohol in the presence of base (e.g., 312 — 322) is typical of Fp+ complexes of acyclic allenes.131132 The thermal chemistry of 312 is unusual in its decomposition to 324 (Scheme 41). This is probably attributable to the presence of the triflate counterion, since the corresponding fluoroborate salt is stable when warmed to 40°C for 16 h.119 A mechanism to 324 via carbene complex 321 appears likely. 

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