- Capping nido-Nonagermanide Clusters with M-PPh3 and Dynamics in Solution: Synthesis and Structure of closo-[(Me3Si)3Si]3Et[Ge9 M](PPh3) (M = Ni, Pt)
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In this work, cluster expansion of nine-atomic germanium clusters with nickel and platinum atoms is reported. The compounds [(Me3Si)3Si]3Et[Ge9Ni](PPh3) and [(Me3Si)3Si]3Et[Ge9Pt](PPh3) are characterized by NMR spectroscopy, elemental analysis, and single crystal X-ray structure analysis. The latter represents the first intermetalloid Ge-Pt cluster with a platinum atom as part of a deltahedron. So far, only one compound of this type has been reported for the homologous Pd. Hence, with these new compounds, metal-coordinated deltahedral Ge9 clusters are now known for the whole triad of group 10 elements. The cluster compounds are accessible by treating [(Me3Si)3Si]3EtGe9 with η2-ethylene-bis-(triphenylphosphine)-nickel(0) and η2-ethylene-bis-(triphenylphosphine)-platinum(0), respectively, in toluene. The crystal structure determination reveals ten-vertex-closo-[Ge9M]-cluster cores (M = Ni, Pt) bearing five exo-bonded ligands. Unlike the nine-vertex-cluster [(Me3Si)3Si]3EtGe9, the penta-functionalized platinum containing cluster compound [(Me3Si)3Si]3Et[Ge9Pt](PPh3) does not show fluctuating behavior in solution over a wide temperature range on the NMR time scale, whereas the [(Me3Si)3Si]3Et[Ge9Ni](PPh3) shows highly dynamic processes in solution at ambient temperature.
- Frischhut, Sabine,Kaiser, Felix,Klein, Wilhelm,Drees, Markus,Kühn, Fritz E.,F?ssler, Thomas F.
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- Reactions of organotin(IV) compounds with platinum complexes. Part II. Oxidative addition of SnRxCl4-x to [Pt(COD)2] and subsequent reactions with tertiary phosphines
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Organotin(IV) compounds SnRxCl4-x (R=Me, Ph; x=4-0) add oxidatively to [Pt(COD)2] (COD=cycloocta-1,5-diene) to yield platinum(II) complexes in which Pt has inserted into the Sn-Cl or Sn-R bonds, displacing one COD entity. The new com
- Al-Allaf, Talal A. K.
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- Synthesis, structure and reactivity of N,O-metallacyclic (dicarbonyldiazene) platinum complexes
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Reaction of cis-Pt(PR13)2Cl2 (R1 = Me, Ph) with diacyl hydrazine R2OCNHNHCOR2 (R2 = Me, Ph) in refluxing ethanol and NaHCO3 afforded platinum diazene diacyl complexes Pt(PR13)2(R2OCNNCOR2) (1, R1 = R2 = Ph; 3, R1 = Me, R2 = Ph; 4, R1 = R2 = Me). Reaction of Pt(PPh3)2(C2H4) with diazene dicarboxylates R2OCNNCOR2 (R2 = OEt, OPri) resulted in the formation of Pt(PPh3)2(R2OCNNCOR2) (2, R2 = OEt; 5, R2 = OPri). Multinuclear NMR spectroscopy on 1-5 revealed that the dicarbonyl-substituted diazene ligand is coordinated asymmetrically, consistent with a five membered Pt-N-N-C-O ring. Compound 5 crystallises from THF-benzene as the solvate Pt(PPh3)2(PriO2CNNCO 2Pri)·(C6H6)2; its X-ray crystal structure shows that the coordination sphere of platinum is essentially square planar and coplanar with the five membered Pt1-O1-C5-N2-N1 ring. The Pt1-O1 distance is 2.027(4) A and the Pt1-N1 distance is 2.050(5) A. The N1-N2 distance is 1.421(6) A while the N2-C5 and C5-O1 distances are 1.273(7) and 1.314(7) A, respectively. Complexes 1-5 show sensitivity towards chlorinated solvents (CH2Cl2, CHCl3) under photolysis conditions, forming the corresponding cis-platinum bis(phosphine) dichloride complexes; the same products are formed in a slower thermal reaction with 2 and 5. Complexes 2 and 5 react photochemically with ethylene in [2H8]THF yielding Pt(PPh3)2(C2H4) but 1, 3 and 4 are inert. Addition of an excess of dppe ligand to 2 and 5 resulted in the displacement of PPh3 and the formation of Pt(dppe)(EtO2CNNCO2Et) and Pt(dppe)(PriO2CNNCO2Pri) [dppe = 1,2-bis(diphenylphosphino)ethane].
- Chan, Danny,Cronin, Leroy,Duckett, Simon B.,Hupfield, Peter,Perutz, Robin N.
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p. 511 - 516
(2008/10/08)
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- Attempted generation of Cp(CO)2Re(μ-H)Pt(PPh3)2[C(CH 3)=CHCH3] from reaction of Cp(CO)2ReH- with (PPh3)3Pt[(E)-C(CH3)=CHCH3] + produces Cp(CO)2Re(cis-CH3CH=CHCH3)
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Previously we proposed Cp(CO)2Re(μ-H)Pt-(PPh3)2[C(CH 3)=CHCH3] (II) as a possible intermediate in the reaction of 2-butyne with Cp(CO)2Re(μ-H)Pt(H)-(PPh3)2 (1) to give Cp(CO)2Re(cis-CH3CH=CHCH3) (cis-2). In an attempt to independently synthesize II, the reaction of K+Cp(CO)2ReH- (3) with (PPh3)3Pt(E)-C(CH3)= CHCH3]+CF3SO3- (cis-4) was studied and conversion to cis-2 was observed, but intermediate II was not detected. The reaction is stereospecific: trans-4 reacted with 3 to produce trans-2. K+Cp(CO)2ReD- (3-d) reacted with trans-Pt[C(CH3)=CH2](CF3SO 3)(PPh3)2 (5) to give Cp(CO)2Re(CH2=CDCH3) (6-d), which demonstrated that 3 is the hydride source in these reactions.
- Casey, Charles P.,Wang, Yan
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- 209. The Coordination Chemistry of 1,2-Bisbenzene with Nickel(II), Palladium(II), Platinum(II), and Platinum(0) and the X-Ray Crystals Structure of benzene)(C2H4)>
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The preparation of complexes (M = Ni, Pd, and Pt; X = Cl, Br, and I; 1 = 1,2-bisbenzene), , (alkene = C2H4 and CH2 = CHCN), and is reported.Their 1H- and 31P-NMR spectra were recorded and used for structural assignments.The X-ray crystal structure of was determined.It is shown that the P-Pt-P bond angle in this complex differs significantly from those found in related compounds with monodentate phosphines, and that this difference is likely to be due to intramolecular contacts.
- Camalli, Mercedes,Caruso, Francesco,Chaloupka, Stanislav,Leber, Ernest M.,Rimml, Heinrich,Venanzi, Luigi M.
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p. 2263 - 2274
(2007/10/02)
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- Metallacyclobutarenes from cyclopropanaphthalene: reactions with rhodium(I), platinum(0) and palladium(0)
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1H-Cyclopropanaphthalene(V) reacts with chlorotris(triphenylphosphine)rhodium(I) and (ethene)bis(triphenylphosphine)platinum(0) with oxidative insertion of the metal into the three-membered ring ?-bond; rhodia- and platina-2H-cyclobutanaphthalenes r
- Stang, Peter J.,Song, Linsheng,Halton, Brian
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p. 215 - 220
(2007/10/02)
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- Simple Synthesis of (η2-Ethen)bis(triphenylphosphane)platinum(0)
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The title compound 2 is easily accessible through reduction of dichlorobis(triphenylphophane)platinum(II) (1) with sodium tetrahydridoborate in ethanol under ethene pressure or without pressure in methylene chloride/ethanol.No nitrogen atmosphere or purified solvents are necessary.
- Nagel, Ulrich
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p. 1998 - 1999
(2007/10/02)
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- Synthesis and Reactivity of Platinum-Formaldehyde Complexes
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Sodium dihydronaphthylide reduction of (R3=Et3, Pri3, Ph3, Et2Ph, or 1/2Ph2PCH2CH2PPh2) under an ethylene atmosphere gives in quantitative yield as shown by (31)P n.m.r. spectroscopy.Reactions of the ethylene complexes with CO, CH2I2, (CF3)2CO, (CO2Et)2CO, and CH2O are described.Monomeric formaldehyde reacts to give the first platinum-formaldehyde complexes, , decomposition of which produces (n=3 or 4) and a complex tentatively assigned as .
- Head, Robert A.
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p. 1637 - 1640
(2007/10/02)
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- ALKYNE COMPLEXES OF PLATINIUM. PART 4. STEPWISE FORMATION OF DI- AND TRI-PLATINIUM COMPLEXES WITH BRIDGING ALKYNE LIGANDS; CRYSTAL STRUCTURE OF
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Reaction of the compound with or (cod=cyclo-octa-1,5-diene) affords diplatinium complexes (R=Ph or Et).The triphenyl-phosphine compound has also been prepared by treating PhCCPh with .The terminal alkyne ligand in bonds a third platinium atom on treatment with to give the triplatinium complex .The latter can also be prepared by addition of 2 mol equivalents of to , and the triethylphosphine-triplatinium analogue is similarly obtained using .In view of the novelty of these compounds, a single-crystal X-ray diffraction study has been carried out on , crystals of which are monoclinic, space group C2/c (no. 15), with Z=4 in a unit cell of dimensions a=17.047 (2), b=13.667 (2), c=25.073 (3) Angstroem, and β=105.79(1)deg.The structure has been solved by heavy-atom methods from 3 038 intensity data =3.0?(I)> measured on a fourcircle diffractometer at 300 K, and refined to R 0.047 (R'0.046).The three platinium atoms adopt an open V-shaped configuration with an internuclear distance of 2.90 Angstroem and an interbond angle of 144deg, while the acetylenic units form transverse bridges across the two Pt-Pt vectors on the convex side of the V.The phenyl groups bend away from the metal atoms to give a C-C-Ph angle of 139deg, and the whole molecule is constrained crystallographically to C2 symmetry.The ethyl groups of the phosphine ligands are ill defined and possibly disordered.The diplatinium complexes (R=Ph or C6F5) have also been prepared, and characterised spectroscopically.Reaction of t)2> with yields trans-t)2(PPh3)2>>, scrambling of the CNBut and PPh3 ligands having occured.The stereochemistry of this complex, and its PhCC6H4OMe-4 analogue, has been established by 31P and 13C-labelling n.m.r. studies.The modes of formation of the various compounds are discussed.
- Boag, Neil M.,Green, Michael,Howard, Judith A. K.,Spencer, John L.,Stansfield, Robert F. D.,at all.
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p. 2182 - 2190
(2007/10/02)
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