15189-53-4Relevant academic research and scientific papers
I+-abstraction versus I--displacement in the reactions of diiodoacetylene with metal carbonyl anions: X-ray structure of CMn(CO)5>
Davies, Julian A.,El-Ghanam, Moneim,Pinkerton, A. Alan,Smith, Douglas A.
, p. 367 - 376 (1991)
Solid diiodoacetylene ICCI, reacts with THF solutions of the highly basic, third row, metal carbonyl anion, Re(CO)5-, exclusively by a formal I+-abstraction process producing ReI(CO)5 and Re2I2(CO)8.Under the same conditions, the less basic, first row, metal carbonyl anion, Mn(CO)5- reacts to produce not only Mn2I2(CO)8 by formal I+-abstraction but also (OC)5MnCCMn(CO)5 by I--displacement.These results may be rationalized by HSAB arguments and consideration of charge distribution in the substrate as indicated by molecular orbital calculations.The X-ray structure of (OC)5MnCCMn(CO)5 is reported.Crystals are triclinic, space group P1, with Z = 1 in a unit cell of dimensions a 6.421(2), b 6.425(2), c 9.520(2) Angstroem, α 81.86(2), β 88.55(2), γ 82.06(2) deg, and Dcalc 1.79 g cm-3.The structure was solved by the Patterson and Fourier methods and refined by full-matrix least squares to R = 0.024, Rw = 0.033 for 1372 observed reflections with Fo2 > 3.0?(Fo2).The complex is centrosymmetric and thus exhibits an eclipsed geometry in the solid state.
Studies of the structures and bonding of gold-bridged dirhenium carbonyl cluster complexes
Adams, Richard D.,Wong, Yuen Onn,Zhang, Qiang
, p. 7540 - 7546 (2014/04/03)
The compounds Re2(CO)8(μ-AuPPh3) 2, 1, a dimer of Re(CO)4(μ-AuPPh3), and ax,ax-Re2(CO)8(PPh3)2 were obtained from UV-vis radiation-induced decarbonylation of the compound Re(CO) 5[Au(PPh3)]. Compound 1 contains two rhenium atoms bridged by two AuPPh3 groups. The complex has 32 valence electrons and is formally unsaturated by the amount of two electrons. The Re-Re bond distance in 1 is unusually short (Re-Re = 2.9070(3) A), as found by a single-crystal structural analysis. The nature of the metal-metal bonding in 1 was investigated by DFT computational analyses, which have provided evidence not only for σ-bonding but also significant complementary π-bonding directly between the two rhenium atoms. The electronic structure of Re2(CO) 8(μ-H)2, 2, was similarly analyzed and is compared with that of 1. Compound 1 is intensely colored due to low-energy, metal-based electronic transitions between the HOMO and HOMO-2 and the LUMO. Compound 1 reacts with I2 to yield Re2(CO)8(μ- AuPPh3)(μ-I), 3, and the known compound Re2(CO) 8(μ-I)2, 4, by substitution of the bridging AuPPh 3 groups with bridging iodide ligands. Compound 3 is electronically saturated, 34 valence electrons, and contains a formal Re-Re single bond: Re-Re = 3.2067(5) A. Compound 3 was also in a high yield (83%) from the reaction of Re2(CO)8(μ-H)(μ-CH=CHC4H9) with Au(PPh3)I. The Re-Re bonding in compounds 3, 4, and Re 2(CO)10 was also analyzed computationally, and this bonding was compared with their bonding in 1 and 2.
A mixed-valence tetranuclear rhenium cluster with Re(I)-Re(III) dative bonds
Calderazzo, Fausto,Poli, Rinaldo,Zanazzi, Pier Francesco
, p. 3942 - 3947 (2008/10/08)
The reaction between Re2I2(CO)8 and S2Ph2 gives Re4I2(SPh)6(CO)8 (2) under forcing conditions. The product has been characterized by X-ray diffractometry: t
