| | 1 | Author
| Ridvan Talay, Dieter Rehder | Requires cookie* | | | Title
| Carbonylvanadium  | | | | Abstract
| , -mangan-und -molybdänkomplexe mit den Liganden o-C6H4EPh2(E Ph2) (E, E = P, As, Sb, Bi) und cis-Ph2PCH=CHPPh2 Carbonylvanadium, -manganese and -molybdenum Complexes of the Ligands o-C6H4EPh2(E'Ph2) (E, E' = P, As, Sb, Bi) and cis-Ph2PCH=CHPPh2 The photo-induced reaction between the complexes [Et4N][V(CO)6] (1), j? 5 -C5H5V(CO)4 (2), f? 5 -C5H5Mn(CO)3 (3) or 7? 5 -C5H5Mo(CO)3CH3 (4) and the ligands o-C6H4EPh2(E'Ph2) (E = E' = P: a; E = P, E'=As: b; E = E'= As: C; E = P, E'=Sb: d; E = P, E'= Bi: e; E = As, E' = Sb: f) and ds-Ph2PCH = CHPPh2 (g), L, yields -depending on the steric requirement of L -the compounds (M}L ({M} = cw-V(CO)4-, eis-CpV(CO)2, CpMn(CO), CpMo(CO)CH3; L = a, b, c, g), {M'}L ({M'j = V(CO)5-, L -d; {M'} -CpV(CO)3, L -d, e; {M'} = CpMn(CO)2, L = e) or mixtures of {M}L and (M'}L ({M}, {M'} = V(CO)4,5, L = e,f; {M}, {M'} = CpV(CO)2>3, L = f). In the mono-substituted species {M'}L coordination (as indicated by the 51 V NMR spectra) occurs through EPh2 and E'Ph2, which is explained by a reaction path via a labile chelate 5-ring structure. Shielding of the 51 V nucleus decreases in the order g > SbPh2 > PPh2 > AsPh2 > BiPh2 (derivatives of 1) and g > SbPh2 > PPh2 > BiPh2 >AsPh2 (derivatives of 2), and is smaller in the rigid chelates incorporating the o-phenylene ligands than in the more flexible structures of phospha-and arsabutane complexes. This fact is discussed in terms of hindered <7-overlap due to distortion of the EVE angle, which also results in an increase of CO valence force constants in rigid chelates. 31 P coordination shifts increase according to dppe < a < g and arphos < b (dppe = Ph2P(CH2)2PPh2, arphos = Ph2As(CH2)2PPh2). 31 P NMR spectra of the molybdenum complexes suggest that the basic geometry for 4 a and 4 b likely is tetragonal pyramidal, while the preferred structure for 4 g appears to be the trigonal bipyramid with the ligand in equatorial positions. The crystal and molecular structure of 1 a is reported. The complex crystallizes in the space group C2/c (a = 2196.0, b= 1080.1, c = 2022.7 pm, ß= 124.6°). The most striking result is the small PVP angle of 80.8 (0.2)°. Optimized methods for the synthesis of the ligands a-f are described; the ligands are characterized by their mass spectra. | | | |
Reference
| Z. Naturforsch. 36b, 451—462 (1981); eingegangen am 4. Dezember 1980 | | | |
Published
| 1981 | | | |
Keywords
| Carbonylphosphinevanadium, Vanadium-NMR, Phosphorus-NMR | | | |
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| default:Reihe_B/36/ZNB-1981-36b-0451.pdf | | | | Identifier
| ZNB-1981-36b-0451 | | | | Volume
| 36 | |
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