Unsaturated Triosmium Carbonyl Cluster Complexes with Bridging Aryl Ligands: Structures, Bonding, and Transformations

Abstract

For the calculations on 2, geometry optimized calculations were performed with ADF2012 program 24 by using the PBEsol functional 1 with scalar relativistic correction and valence quadruple-ζ + 4 polarization, relativistically optimized (QZ4P) basis sets for osmium and gold and valence double-ζ function (DZ) basis sets for the phosphorus, carbon, oxygen, and hydrogen atoms with no frozen cores. The molecular orbitals for 2 and their energies were determined by a geometry optimized calculations that were initiated with the structures as determined from the crystal structure analyses. The fragment analysis for 2 was also performed with the ADF programs by using the meta-Generalized Gradient Approximation (meta-GGA) level nonempirical Tao-Perdew-Staroverov-Scuseria (TPSS) functional. 2 The phenyl group was used as one fragment and the other fragment was the complete molecule minus the phenyl group. The MOs of the fragments were then calculated by using the same basis sets as described above.For the calculations of 3b, geometry optimized calculations were performed with ADF2012 program 1 by using the PBEsol functional with scalar relativistic correction and valence triple-ζ +polarization, relativistically optimized (TZP) basis sets, with small frozen cores. The molecular orbitals and their energies were determined by geometry optimization

Binuclear Aromatic C−H Bond Activation at a Dirhenium Site

“…An ORTEP diagram of the molecular structure of 3 is shown in Figure 2. In 3,the naphthyl ligand serves as athree-electron donor, thus the rhenium atoms are formally electronically saturated and as ar esult, the Re À Re bond distance,3 .0531(3) , is significantly longer than that in the unsaturated 2.Asimilarly coordinated m-h 2 -naphthyl ligand was recently structurally characterized as one of two isomers of the triosmium complex [Os 3 (CO) 10 [7] Most interestingly,itwas found that 1 reacts with C 6 D 6 to produce its deuterated equivalent [D 6 ]-1 in quantitative yield within 11 hours at 60 8 8C[ Equation (3)]. Then aphthyl ligand was formed by the elimination of benzene from 1 and the oxidative addition of naphthalene at aC À Hb ond at the 2-position.…”

Organometallic chemistry of pentaruthenium-gold carbonyl cluster complexes

“…Two of the Au(PPh 3 ) groups form a mutually bonded pair on the Ru1-Ru2-Ru3 face and Ru2-Ru3 edge of the square pyramid, Au1-Au2 = 2.8277(6) Å, similar to that found in 9. An additional Au(PPh 3 ) group, Au4, is found along the Ru4 -Ru5 edge of the Ru 5 square base and for the fourth Au(PPh 3 ) group, atom Au3, is asymmetrically bonded across the square base and includes bonding to the interstitial carbido ligand C0, Ru2-Au3 = 3.1831 9 11, Ru1-Ru4 = 2.8498 10, Ru2-Ru5 = 2.8148 11Ru2-Ru3 = 3.0316 (10),Ru3-Ru4 = 2.7968 10, Ru4-Ru5 = 3.0933 10, Ru1-Au1 = 2.8728 9, Ru2-Au1 = 2.8609 9 8, Au3-C0 = 2.126 (8).…”

“…Eqs. (1) -(3) [7][8][9]. In some cases, the aryl ligands have adopted unusual bridging coordination modes that can result in interesting physical and chemical properties, such as hindered rotation about the metal-metal bond [10].…”

Synthesis, structure and bonding of a digold complex with bridging triphenylstannyl ligands

“…Examples with terminally-coordinated tin ligands include Au(PMe 2 Ph) 2 (SnCl 3 ), 1, Au -Sn = 2.881(1) Å [6] and Au(PPh 3 )[Sn{N(p-tol)SiMe 2 } 3 SiMe], 2, [7], see Scheme 1. We have recently found that aryl containing gold phosphine complexes, Au(PPh 3 )Ar, Ar = Ph, Np, Py, react with certain dirhenium [11] and triosmium [12] carbonyl complexes to yield electronically unsaturated complexes containing bridging aryl ligands. In the present work, we have investigated the reaction of Au(PPh 3 )Ph with HSnPh 3 .…”