Untitled

Abstract

The photo‐induced substitution of a CO ligand has been used to prepare the halfsandwich complexes (η3‐C3H5)V(CO)4[P(C7H7)3] (1), (η5‐C5H5)V(CO)3[P(C7H7)3] (2), (η7‐C7H7)V(CO)2[P(C7H7)3] (3), (η6‐C6H3Me3)Cr(CO)2[P(C7H7)3] (4), and (η5‐C5H5)Mn(CO)2[P(C7H7)3] (7), in which the olefinic phosphane is coordinated as a conventional two‐electron ligand through the lone pair of electrons at phosphorus. Some analogues, which are permethylated at the aromatic ring (2*, 4*, 7*), were included for comparison. Subsequent photo‐elimination of another CO group from 4 or 7 converts the olefinic phosphane into a chelating four‐electron ligand, leading to (η6‐C6H3Me3)Cr(CO)[P(C7H7)2(η2‐C7H7)] (5) and (η5‐C5H5)Mn(CO)[P(C7H7)2(η2‐C7H7)] (8), respectively. The η2‐coordinated double bond in 5 and 8 can be displaced by trimethylphosphite to give (η6‐C6H3Me3)Cr(CO)[P(C7H7)3][P(OMe)3] (6) and (η5‐C5H5)Mn(CO)[P(C7H7)3][P(OMe)3] (9). The 31P and 13C NMR spectra of all complexes are discussed, and X‐ray structure analyses for 2 and 8 are presented. Prolonged irradiation of 7 and 8 led to a di(cycloheptatrienyl)phosphido‐bridged dimer, {(η5‐C5H5)Mn(CO)[P(C7H7)2]}2(10).

Facile Access to Transition‐Metal–Carbonyl Complexes with an Amidinate‐Stabilized Chlorosilylene Ligand

“…The downfield‐shifted resonance in complex 1 compared to the uncomplexed ligand L ( δ =14.6 ppm)8 is due to the coordination of silicon to the vanadium. The 51 V NMR spectrum of complex 1 exhibits a single resonance at δ =−1520.02 ppm, which is consistent with those of other reported vanadium(I) species 11. The 13 C NMR spectrum reveals the presence of carbonyl groups with a broad resonance at δ =260.35 ppm.…”

Synthesis and reactivity of germyl complexes of manganese and rhenium

“…The coordination polyhedron around the manganese may be defined as an octahedron, but some distortion is found in the carbonylmanganese-carbonyl axis, with a C(1)eMneC(2) angle of 162.7(1) , bent toward the position occupied by the germyl ligand. This feature had already been seen in similar compounds, like the related complex Mn(SnH 3 )(CO) 3 [PPh(OEt) 2 ] 2 [10a] or the dinuclear complex [Mn 2 (CO) 10 {P(C 7 H 7 ) 3 } 2 ] [28]. The other two axes are almost linear [178.30(3) and 176.11(9) )].…”

1:1 Adducts of Copper(I) and Silver(I) Halides with the Olefinic Phosphane Tri(1‐cyclohepta‐2, 4, 6‐trienyl)phosphane. Molecular Structures of CuX[P(C7H7)3] (X = Cl, Br), AgCl[P(C7H7)3] and {Cu(μ3‐I)[P(C7H7)3]}4

“…The NMR spectra of the new complexes (Table 1) show the typical pattern of the olefinic phosphane ligand, similar to that of the uncoordinated phosphane P(C 7 H 7 ) 3 (1) [cf. 29,30]. It can be assumed that the cyclohepta-2,4,6-trienyl substituents in the adducts 2a-c and 3c are non-rigid in solution.…”

“…The Cu-C distances in these compounds are found in the range of 200-215 pm. Similar Cu-C bond distances are observed in the solid state structures of the allyl cyanides Cu 2 X 2 ·(CH 2 ϭCH-CH 2 CN) (X ϭ Cl [37,38] and Br [37]), of the 1:1 adducts CuCl·olefin where the πcoordinated alkene derivative may be either acrylic acid [39] or acryl amide [40], and of the allyl amine π-complexes CuX(CH 2 ϭCH-CH 2 NH 2 ) (X ϭ Cl, Br) [ [29]. The molecular structure of the tetrameric copper(I) iodide, {Cu(µ 3 -I)[P(C 7 H 7 ) 3 ]} 4 (2c), corresponds to that of the highly distorted cubane framework of the iodides [45].…”