Phosphine complexes structures

Assefa, Z Forward, J.M., Grant T.A., Staples, R.J., Hanson, B.E., Mohamed, A.A. and Fackler, J.P. Jr (2003) Three-coordinate, luminescent, water-soluble gold(l) phosphine complexes structural characterization and photoluminescence properties in aqueous solution. Inorganica Chimica Acta, 352, 31 5. 

The reduction of allyl chlorides and acetates with sodium formate is efficiently catalyzed by hydrophilic phosphine complexes (Structures 1-3) under water-hep-... 

The phosphine complex Ru(dmpe)2 has been studied in matrices [62], Ru(diphos)2 (diphos = depe, dppe, (QFs P F P Fs ) has similarly been formed by photolysis of Ru(diphos)2H2 in low-temperature matrices. They probably have square planar structures and undergo oxidative addition with cobalt, C2H4 and hydrogen [63]. 

The structures of the two tri(n-butyl)phosphine complexes of this type have been determined (Figure 2.58), again showing the high trans-influence of PR3 compared with Cl (Figure 2.58). 

A number of tertiary phosphine complexes with bulky ligands (Figure 3.80) have modified square pyramidal structures, examples being M(I)3Br2, Pt(II)3Br2 and Pd(III)3Br2 (all X-ray) [136]. 

Figure 3.115 (a) Syntheses of organoplatinum phosphine complexes (b) structures of methyl-platinum phosphine complexes. 

The soft Au+ forms relatively few complexes compared with those of phosphines. Complexes with ammines, nitriles and diazoles like Au(NH3)2 and Au(RCN)2 are known but little studied. In linear Au(NH3)2, Au-N is 2.01-2.03 A [70a], [Au(NCPh)2]+ has been used as a labile source of other gold complexes [70b]. AuCl(piperidine) is a monomer with weak tetra-meric association in contrast AuX(py) (X = Cl, Br, I) are [Aupy2]+[AuX2] with a chain structure in the solid state (and Au-Au interactions), suggesting a close balance between factors for molecular and ionic structures [70c] (note also the tetrahydrothiophene complexes in section 4.10.6). 

Uranium. tetrathiocyanatotetrakis[tris-(dimethylamino)phosphine oxide]-structure, 1.87 Uranium carbide nuclear fuels dissolution, 6, 928 Uranium complexes, 3,1131-1215 carbamic acid... 

The iridium phosphine complex [IrC PEt,),] 39b can also activate O-H bonds of carboxylic acids. The stoichiometric reaction with a,(o-alkynoic acids RC=C(CH2)2 CO2H (R = Me, Ph) gave cis-hydrido(carboxylato)iridium(III) complexes 92 (Eq. 6.26), and the molecular structure of 92a was determined crystallographically [59]. 

Tetrakisphosphine complexes of Ni° are usually prepared either from labile Ni° precursors (such as [Ni(cod)2] or [Ni(CO)2(cod)]) or by reduction of an appropriate Ni11 complex in the presence of phosphine. Despite the large number of homoleptic Ni-phosphine complexes NiL4, however, relatively few X-ray crystal structures are known. Some examples are collected in Table 23. Typical Ni°—P distances are in the range 2.14-2.21 A. [Ni(PMePh2)4] was obtained serendipit-ously upon treatment of [NiBr(NPMe3)]4 with LiCCPh. 

A number of zinc phosphine complexes have been synthesized due to interest in chemical vapor deposition for example, Zn(S-2,4,6-tBuC6H2)2(Ph2PMe) and [ZnI2(PEt3)]2.295 304 The structure of bis[(diphenylphosphino)propyl] zinc shows a highly distorted tetrahedral environment with an alkyl and a phosphorus donor binding from each bidentate ligand.318... 

In a thorough work with an extensive literature survey, crystal structures, vibrational and 31P NMR spectra of several phosphine complexes of mercury(II) halides HgX2 are presented.235 In the dibenzophosphole complex (dbp)2HgBr2, Hg adopts a distorted tetrahedral coordination (rav(Hg—P) 250.2, rav(Hg—Br) 261.1pm) (cf. the related Cd complex in the previous paragraph), with slightly shorter Hg—P and Hg—Br bonds, respectively, than in the comparable... 

Bismuth phosphine complexes represent a substantial component of the established phosphine complexes of heavier p-block elements, and an excellent overview has presented an important bonding model for these systems (7). The observed structures are considered as trigonal-pyramidal BiX3 units with three secondary trans bonds. If the acceptor orbitals are the Bi-X trans arrangement is expected, as the relationship between the trans X-Bi-P bond distances. The shortest Bi-P distance [2.7614(2) vs 2.866(3) A] is trans to the longer Bi-Br distance [3.403(1) vs 2.9916(1) A], as the only arrangement that will allow the phosphine ligands to occupy trans... 

Ellis, J.W., Harrison, K.N., Hoye, P.A.T., Orpen, A.G., Pringle, P.G., and Smith, M.B., Water-soluble tris(hydroxymethyl)phosphine complexes with nickel, palladium, and platinum. Crystal structure of Pd P(CH2OH)3 4].cntdot.CH3, Inorg. Chem., 31, 3026, 1992. 

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