Organometallics versus P4 Complexes of Group 11 Cations: Periodic Trends and Relativistic Effects in the Involvement of (n-1)d, ns, and np Orbitals in Metal-Ligand Interactions
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We have applied D. Functional Theory (DFT) at the generalized gradient approxn. (GGA) level to investigate the C-S bond cleavage in hexathioether complexes of the form [M(9S3)2]n+ (with 9S3 = 1,4,7-trithiacyclononane and M = Re, Tc; n = 1, 2; as well as M ...
The photocycle of aqueous ruthenium-(trisbipyridine) [Ru(bpy)3]2+ was studied under high laser excitation intensities and high sample concentrations with picosecond resolved x-ray absorption spectroscopy. In a pump-probe scheme a femtosecond laser pulse pr ...
We present first-principles mol. dynamics studies of the reductive C-S bond cleavage reaction in hexathioether complexes of the form [Re(9S3)2]m+ (with 9S3 = 1,4,7 trithiacyclononane and m = 1,2). Our calcns. show that electron transfer and bond dissocn. t ...
To accelerate reactive events in mol. dynamics simulations we introduce a general bias potential scheme which depends only on the electronic degrees of freedom of the reactive system. This electronic reaction coordinate, which is expressed in terms of a pe ...
Three immobilized Cu(II) complexes were generated by the following: (a) homopolymerization of the N,N',N '' chelate ligand tris[2-(1-vinylimidazolyl)]phosphine (1) and subsequent metalation with CuCl2; (b) copolymerization of 1 with ethyleneglycol dimethac ...
The silver, copper and gold complexes of tripodal N-heterocyclic carbene (NHC) ligand, 1,1,1-tris[(3-methylimidazol-1-yl-2-ylidene)methyl]ethane were prepd. and characterized. The silver complex of the title ligand, TIMEMe was prepd. by reaction of [H3TIME ...
Reactions of tBuP(NH2)2 with Group 13 trialkyls MR3 (M = Al, Ga, In; R = Me, tBu) were investigated in detail. According to variable-temp. (VT) NMR investigations, the reaction proceeds stepwise with the initial formation of aminophosphane adducts, which s ...
New methods that allow the generation of transition metal-based catalysts and receptors are discussed. It is shown that heterobimetallic, halogeno-bridged complexes are well-suited for screening assays in combinatorial catalysis. Metal catalysts with a str ...
The reaction of [RuCl3(AsPh3)(2)(MeOH)] with the dimeric complexes (cod)RhCl, (ppy)RhCl (ppy = cyclometalated 2-phenylpyridine), (cymene)RuCl2 and CP*MCl2 (M = Rh, Ir) has been investigated. The structure of the resulting products was s ...
This paper is aimed at introducing the organometallic chemist to the fascinating area of organometallic pharmaceuticals. It commences by identifying the properties of organometallic (transition metal) compounds that lend themselves to medical applications. ...