Rhodium(I) complexes of α-keto-stabilised 1,2-bis(diphenylphosphino)alkane mono ylides
Rhodium(I) complexes of the hybrid ylide-phosphine ligands, Ph2P(CH2)nPPh2(CHC(O)C6H5) (n = 1: dppm-yl, or 2: dppe-yl) have been synthesised from [Rh(μ-C1)(COD)]2 (COD = 1,5-cyclooctadiene) and characterized by NMR spectroscopic and X-ray structural methods. The dppe-yl behaves as an ambidentate ligand; it functions as a monodentate P-donor ligand with a dangling ylidic carbon in the neutral chloro complex, [(COD)Rh(Cl)(dppe-yl)] (1), whereas replacement of the chloride by a non-coordinating counter anion results in the formation of the complexes, [(COD)Rh(L-L’)]+ (L-L’ = dppe-yl (2) or dppm-yl (3)) respectively in which the ligands are bonded to the metal via the phosphorus and the ylidic carbon atoms. The 1,5-cyclooctadiene (COD), present in the Rh(I) precursor, remains intact in the products. The structures of1,2 and3 have been confirmed by X-ray crystallography.
Structural, Theoretical, and Spectroscopic Study of Mercury(II) Complexes of two New Unsymmetric Phosphorus Ylides
Abstract The reaction of Ph2PCH2PPh2 (dppm) with 4-methylphenacyl bromide and 2-(bromoacetyl)naphthalene in chloroform produce the new phosphonium salts [Ph2PCH2PPh2CH2C(O)C6H4Me]Br (1) and [Ph2PCH2PPh2CH2C(O)C10H7]Br (2). Further, by reaction of the monophosphonium salts of dppm with the strong base Et3N the corresponding bidentate phosphorus ylides, Ph2PCH2P(Ph)2 = C(H)C(O)C6H4Me (3) and Ph2PCH2P(Ph)2 = C(H)C(O)C10H7 (4) were obtained. The reaction of these ligands with mercury(II) halides in dry methanol led to the formation of the mononuclear complexes {HgX 2[(Ph2PCH2PPh2C(H)C(O)C6H4Me)]} [X = Cl (5), Br (6), and I (7)] and {HgX 2[(Ph2PCH2PPh2C(H)C(O)C10H7)]} [X = Cl (8), Br (9), and I (10)]. Characterization of the obtained compounds was performed by elemental analysis, IR, 1H, 31P, and 13C NMR spectra. The structure of compounds 3 and 10 are unequivocally determined by single crystal X-ray diffraction techniques. X-ray analysis of 10 reveals the presence of mononuclear complex containing Hg atom in a distorted tetrahedral environment. In all complexes, the title ylides are coordinated through the ylidic carbon and the phosphine phosphorus. Computational studies on ligand 4 and complexes 8, 9, and 10 at DFT (B3LYP) level of theory are also reported. It was shown that the formation of P,C-coordinated 1+1 complex 10 is energetically more favored than corresponding P,P-coordinated 1+2 product. [Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the following free supplemental files: Additional figures] GRAPHICAL ABSTRACT
Coalition for the International Criminal Court Questionnaire to Candidates for the Position of Registrar of the International Criminal Court Conscious of the critical importance of the Registrar of the ICC
As an independent judicial institution in the emerging international justice system, the International Criminal Court will:  Fairly, effectively and impartially investigate, prosecute and conduct trials of the most serious crimes;  Act transparently and efficiently; and  Contribute to long lasting respect for and enforcement of international criminal justice, to the prevention of crime and to the fight against impunity