Electronic spectroscopy of homo- and heterometallic binuclear coinage metal phosphine complexes in isolation.

Binuclear coinage metal phosphine complexes are examined under ion trap isolation in order to elucidate their noncovalent binding, structural properties and intrinsic electronic spectra. Our survey shows an intriguing order of electronic transitions obtained by in situ synthesis and mass-spectrometrically supported UV photodissociation spectroscopy on a series of six isolated homo- and heterobinuclear complexes of type [MM'(dcpm)2]2+ (M, M' = CuI, AgI, AuI; dcpm = bis(dicyclohexyl-phosphino)methane). This approach provides the unique opportunity to study all possible coinage metal interactions within a fixed ligand framework. A successive blue-shift (33 700-38 500 cm-1; 297-260 nm) of the lowest-energy bright electronic transition energy in gas phase was observed in the order of Cu2 < CuAu < CuAg < Au2 < AgAu < Ag2. This order was reproduced by quantum chemical calculations using a scalar-relativistic GW-Bethe-Salpeter-equation (GW-BSE) approach. Theory ascribes the electronic bands of all complexes to metal-centered 1MC(dσ*-pσ) transitions revealing a strengthening of metal-metal' (M-M') binding upon excitation, in agreement to mass spetrometric results. A test of the correlation of transition energies with M-M' distance by quantum chemical calculations of single point energies as a function of intermetallic distance indicates qualitative agreement with experimental results. However, the experimentally observed high sensitivity of spectroscopic shifts towards metal composition cannot be accounted for solely by M-M' distance variation. The differences in electronic transitions are qualitatively rationalized by the varying (n + 1)s (n = 3, 4, 5) orbital contributions (increase from Cu2via CuAu/CuAg to Au2/AgAu/Ag2) within the nd(n + 1)s/p-hybridization for the ground electronic state of the different complexes, whereas the excited state (of (n + 1)p orbital character) shows significantly less variation in energy. In particular, the observed spectroscopic and mass spectrometric sequence for the Ag/Au complexes is traced back to the interplay of Pauli repulsion and variation in metal-ligand bond strength within the orbital hybridization model.

Heterolytic Si-H Bond Cleavage at a Molybdenum-Oxido-Based Lewis Pair.

The reaction of a molybdenum(VI) oxido imido complex with the strong Lewis acid B(C6 F5 )3 gave access to the Lewis adduct [Mo{OB(C6 F5 )3 }(NtBu)L2 ] featuring reversible B-O bonding in solution. The resulting frustrated Lewis pair (FLP)-like reactivity is reflected by the compound's ability to heterolytically cleave Si-H bonds, leading to a clean formation of the novel cationic MoVI species 3 a (R=Et) and 3 b (R=Ph) of the general formula [Mo(OSiR3 )(NtBu)L2 ][HB(C6 F5 )3 ]. These compounds possess properties highly unusual for molybdenum d0 species such as an intensive, charge-transfer-based color as well as a reversible redox couple at very low potentials, both dependent on the silane used. Single-crystal X-ray diffraction analyses of 2 and 4 b, a derivative of 3 b featuring the [FB(C6 F5 )3 ]- anion, picture the stepwise elongation of the Mo=O bond, leading to a large increase in the electrophilicity of the metal center. The reaction of 3 a and 3 b with benzaldehyde allowed for the regeneration of compound 2 by hydrosilylation of the benzaldehyde. NMR spectroscopy suggested an unusual mechanism for the transformation, involving a substrate insertion in the B-H bond of the borohydride anion.

Intermetallic Competition in the Fragmentation of Trimetallic Au-Zn-Alkali Complexes.

Cationization is a valuable tool to enable mass spectrometric studies on neutral transition-metal complexes (e.g., homogenous catalysts). However, knowledge of potential impacts on the molecular structure and catalytic reactivity induced by the cationization is indispensable to extract information about the neutral complex. In this study, we cationize a bimetallic complex [AuZnCl3 ] with alkali metal ions (M(+) ) and investigate the charged adducts [AuZnCl3 M](+) by electrospray ionization mass spectrometry (ESI-MS). Infrared multiple photon dissociation (IR-MPD) in combination with density functional theory (DFT) calculations reveal a µ(3) binding motif of all alkali ions to the three chlorido ligands. The cationization induces a reorientation of the organic backbone. Collision-induced dissociation (CID) studies reveal switches of fragmentation channels by the alkali ion and by the CID amplitude. The Li(+) and Na(+) adducts prefer the sole loss of ZnCl2 , whereas the K(+) , Rb(+) , and Cs(+) adducts preferably split off MCl2 ZnCl. Calculated energetics along the fragmentation coordinate profiles allow us to interpret the experimental findings to a level of subtle details. The Zn(2+) cation wins the competition for the nitrogen coordination sites against K(+) , Rb(+) , and Cs(+) , but it loses against Li(+) and Na(+) in a remarkable deviation from a naive hard and soft acids and bases (HSAB) concept. The computations indicate expulsion of MCl2 ZnCl rather than of MCl and ZnCl2 .

P,C-bond cleavage in the ligand sphere of a nickel(II) complex.

Reacting nickel(ii)perchlorate with a bidentate P,N-ligand in methanol leads to P,C-bond cleavage and gives a five-coordinate nickel complex wherein the nickel(ii) site is coordinated by a tridentate P,N,P-ligand and a bidentate N,C-ligand. The carbanion of the latter is the result of the P,C-bond cleaving process. The diamagnetic nickel(ii) complex was characterized by means of elemental analysis, NMR spectroscopy, cyclic voltammetry and X-ray structure analysis.