Vanadium complexes phosphinates

The activation parameters and dependence on L are shown in Table 13. These data are fully consistent with an associative reaction. The 17-electron complex V(CO)6 has an associative substitution reaction rate that is > 10 ° more facile than for the 18-electron Cr(CO)6 complex. The vanadium complexes are among the most inert of the 17-electron complexes. Table 14 shows the rate constants for substitution of several complexes. As expected from size considerations, substituting a phosphine ligand for a CO decreases the rate for an associative reaction. 

Thermolysis of ()) -cyclopentadienyl)bis(neopentyl)(tri-methylphosphine)vanadium(I) (82) in the presence of 1,2-bis(dimethylphosphuio)ethane leads to the formation of the Schrock-type see Schrock-type Carbene Complexes) alkylidene vanadium complex (83), which is supported by X-ray crystallographic analysis (Scheme 45). " The imido vanadium complex (84) is converted to the corresponding alkylidene complex (86) on treatment with ben-zylidene(triphenyl)phosphorane (85) via substitution of the phosphine ligand (Scheme 46). ... 

SNC, Thiocyanate, gold comiriex, 26 90 SN03C7H, l,2-Benzisothiazifi-3(2lf>-one 1,1-dioxide, chromium and vanadium complex, 27 307. 309 SOOsPCsgH43, Osmium, carbonyl-(thiocarbonyQiiisfttiplienyl-phosphine)-, 26 187... 

Although trialkyl- and triarylbismuthines are much weaker donors than the corresponding phosphoms, arsenic, and antimony compounds, they have nevertheless been employed to a considerable extent as ligands in transition metal complexes. The metals coordinated to the bismuth in these complexes include chromium (72—77), cobalt (78,79), iridium (80), iron (77,81,82), manganese (83,84), molybdenum (72,75—77,85—89), nickel (75,79,90,91), niobium (92), rhodium (93,94), silver (95—97), tungsten (72,75—77,87,89), uranium (98), and vanadium (99). The coordination compounds formed from tertiary bismuthines are less stable than those formed from tertiary phosphines, arsines, or stibines. 

Oxovanadium(IV) complexes with dithiophosphate ligands have been extensively examined <8,121.161,252,386) x typical ESR spectrum is shown in Fig. 7. In addition to the eight vanadium 1=112 hyperfine lines phosphorus (/ = 1/2) superhyperfine splitting is also observed. The phosphorus superhyper-fine splitting can be considered a bit unusual since the phosphorus is located about 3 A or more away from the metal ion. P and As superhyperfine splitting has been observed in the ESR spectra of ill-defined vanadium phosphine 388) and arsine 389) complexes but in those cases, presumably, direct V-P and V—As interactions occur. ESR parameters have been tabulated for a large number of dithiophosphate 121,252) dithiophosphinate 121.252) complexes. Evaluation 3i) of the fractional 3s character of unpaired electron in dithiophosphate complexes yielded a value of 1.35%. The vanadyl(IV) complexes possess approximate C2V symmetry. The unpaired d electron resides... 

The most active d metal peroxo complexes toward nucleophilic substrates, like amines, phosphines, thioethers, double bonds etc., are molybdenum, tungsten and rhenium derivatives vanadium and titanium catalysis is also important, in particular when... 

Direct addition of PF3 to 5-pentadienyl metal complexes offers an alternative synthetic route (method G) and this has been reported in the case of the formation of bis(2,4-dimethylpentadienyl)trifluoro-phosphine complexes of titanium and vanadium [M(C7H11)2PF3] (M = Ti, V) (Scheme 11) 111). 

Complexes containing vanadium in low oxidation states, apart from organometallic compounds, are known with ligands such as bipy, phen, nitric oxide, and tertiary phosphines, which stabihze such oxidation states. Depending on their electronic structure, V and V complexes may be diamagnetic, which permits study by NMR spectroscopy, and EPR spectroscopy has been used to study paramagnetic V complexes. 

Scalar coupling between and has been reported for phosphine and trialkyl phosphite coordinated vanadium carbonyl complexes. (194) V( V- P) typically ranges from 150 to 350Hz. No stereochemical specificity was found, however. 

Apart from the compounds already mentioned, vanadium, manganese, and cobalt chlorides, tetra-alkoxy derivatives of titanium, acetylacetonates of V, Cr, Mo, Mn, and Ni, Cp derivatives of Zr and Nb, and triphenyl phosphine complexes of Ti and Fe were found to be active. Later lanthanide complexes were included in the list of dinitrogen-reducing systems, the most effective being compounds of samarium and yttrium. 

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