- A CONVENIENT SYNTHESIS OF BIS(TRI-t-BUTYLPHOSPHINE)PLATINUM(0) AND ITS OXIDATIVE ADDITION AND LIGAND EXCHANGE REACTIONS
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Pt2 (I) is prepared in high yield from a facile reaction of P(t-Bu)3 with K2PtCl4.Its oxidative addition reactions with CHCl3, CH2Cl2, MeI, and I2, and substitution reactions with CO, M(CO)6 (M=Cr, Mo, W), and t-BuNC have been investigated.Reaction with CHCl3 affords trans-PtHCl2 (II) and (III), and reaction with CH2Cl2 yields (IV).Pt2Me2(μ-I)22 (VI) and P(t-Bu)3MeI are formed in the reaction of I with MeI.VI undergoes intramolecular metalation to give (V), and CH4.Reaction of I with I2 results in the formation of V, trans-PtHI2 (VII) and P(t-Bu)3I2.CO readily displaces one phosphine from I to give Pt33(CO)3 (VIII).I reacts with M(CO)6 to afford VIII and M(CO)5P(t-Bu)3. t-BuNC replaces both the phosphines from I to give Pt3(t-BuNC)3(μ-t-BuNC)3 (IX).
- Goel, Ram G.,Ogini, William O.,Srivastava, Ramesh C.
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- Lewis acid-base interactions between platinum(II) diaryl complexes and bis(perfluorophenyl)zinc: Strongly accelerated reductive elimination induced by a Z-type ligand
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Z-type interactions between bis(perfluorophenyl)zinc and platinum(ii) diaryl complexes supported by 1,10-phenanthroline (phen), 2,2′-bipyridine (bpy), and bis(dimethylphosphino)ethane (dmpe) ligands are reported. In the solid state, the nature of the Pt-Zn interaction depends on the bidentate ligand; the phen-supported complex exhibits an unsupported Pt-Zn bond, while the dmpe derivative features additional bridging aryl interactions. A strongly accelerated rate of reductive elimination is observed for phen- and bpy-supported complexes, while aryl exchange between Pt and Zn is observed for the dmpe complex.
- Liberman-Martin, Allegra L.,Levine, Daniel S.,Ziegler, Micah S.,Bergman, Robert G.,Tilley, T. Don
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supporting information
p. 7039 - 7042
(2016/06/09)
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- A Molecular Rotor Possessing an H-M-H "spoke" on a P-M-P "axle": A Platinum(II) trans-Dihydride Spins Rapidly even at 75 K
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A new class of low-barrier molecular rotors, metal trans-dihydrides, is suggested here. To test whether rapid rotation can be achieved, the known complex trans-H2Pt(PtBu3)2 was experimentally studied by 2H and 195Pt solid-state NMR spectroscopy (powder pattern changes with temperature) and computationally modeled as a tBu3P-Pt-PtBu3 stator with a spinning H-Pt-H rotator. Whereas the related chloro-hydride complex, trans-H(Cl)Pt(PtBu3)2, does not show rotational behavior at room temperature, the dihydride trans-H2Pt(PtBu3)2 rotates fast on the NMR time scale, even at low temperatures down to at least 75 K. The highest barrier to rotation is estimated to be ~3 kcal mol-1, for the roughly 3 ? long rotator in trans-H2Pt(PtBu3)2.
- Prack, Ernest,Okeefe, Christopher A.,Moore, Jeremy K.,Lai, Angel,Lough, Alan J.,Macdonald, Peter M.,Conradi, Mark S.,Schurko, Robert W.,Fekl, Ulrich
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supporting information
p. 13464 - 13467
(2015/11/10)
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- Unexpected substitution reactions of bis(phosphine)platinum ethene complexes
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Reaction of [Pt(C2H4)(PR3)2] (R = Ph or C6H4Me-4) with moderately bulky phosphines at low temperatures did not give the expected tris- or tetrakis-phosphine complexes. Instead, mixed-phosph
- Chaloner, Penny A.,Broadwood-Strong, Gillian T. L.
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p. 1039 - 1043
(2007/10/03)
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- Electronic absorption and MCD spectra for isoelectronic linear two-coordinate bis(tri-tert-butylphosphine)metal complexes of platinum(0) and gold(I)
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Electronic absorption and magnetic circular dichroism (MCD) spectra are reported for Pt(P(t-Bu)3)2 in CH3CN and in n-hexane solution for [Au(P(t-Bu)3)2]ClO4 in CH3CN solution. The intense bands observed from 2.4 to 4.5 μm-1 for the Pt(0) complex and from 4.0 to 5.0 μm-1 for the isoelectronic Au(I) complex are assigned as d → p/metal to ligand charge-transfer (MLCT) transitions to Πu and Σu+ spin-orbit states of 5d → 1πu excited configurations. The red shift in the spectra for the Pt(0) complex compared to the spectra for the Au(I) complex is interpreted in terms of lower metal orbital stability and a smaller 5d-6p energy separation for Pt(0). Detailed spectral assignments lead to the conclusion of minimal involvement of the 5d orbitals in M-P bonding for both complexes.
- Jaw, Huey-Rong C.,Mason, W. Roy
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p. 4370 - 4373
(2008/10/08)
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- PROTONATION OF TERTIARY PHOSPHINE PLATINUM(0) COMPLEXES BY AMMONIUM ION. CHARACTERIZATION AND SOME REACTIONS OF THE RESULTING HYDRIDES
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The platinum(0) complexes Pt(PR3)2 (R3=(t-Bu)3 and (t-Bu)2Ph) react readily with the ammonium salts NH4X (X=PF6 and ClO4) to give the cationic ammine hydrides trans-X.Reaction of Pt(PPH3)3 with NH4PF6 affords PF6.The ammine hyd
- Goel, Ram G.,Srivastava, Ramesh C.
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p. 303 - 310
(2007/10/02)
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- Preparation, characterization, and some reactions of hydridobis(tri-tert-butyl)phosphineplatinum(II) cation containing three-coordinate platinum
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Removal of the chloride ligand from trans-PtHCl2 by a noncoordinating anion affords the complexes trans-2>X (X = PF6, BF4, ClO4, SO3CF3), 1a, 1b, 1c, and 1d respectively, which contain the cationic hydride in which platinum is formally three-coordinate.Complexes 1 react with several ?-donor neutral ligands, L, to give the square-planar complexes trans-2>X.No reaction occurs with H2C=CH2 or F2C=CF2 but (NC)2C=C(CN)2 reacts with 1c to give an air-stable complex trans-2>ClO4 which is indicated to contain ?-bonded (NC)2C=C(CN)2.Neither PhCCPh nor MeO2CCCCO2 reacts with 1 but HCCH seems to react reversibly to form the for-coordinate species trans-CH)2>+, which could not be isolated.In marked contrast to the behaviour of rpeviosly reported cationic platinum(II) hydrides, addition of an equivalent of PCy3 of P(t-Bu)3 to an acetone solution of 1 results in its deprotonation and gives the platinum(0) complex Pt2 quantitatively.Deprotonation of 1 also occurs upon treatment with NH3, Me2S, and NaOMe in acetone.
- Goel, Ram G.,Srivastava, Ramesh C.
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p. 1352 - 1360
(2007/10/02)
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- Preparation, characterization, and some reactions of Bls(tri-tert-butylphosphine)hydrldoplatinum(II) complexes
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Treatment of Pt[P(t-Bu)s]s with protic acids, HX, affords the monohydrides trans-analegues by metathesis. The dihydride la undergo intramolecular metalation, at room temprature, to give the metalated complexes trans.
- Goel, Ram G.,Oginl, William O.,Srivastava, Ramesh C.
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p. 819 - 824
(2008/10/08)
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- Elementorganische Amin/Imin-Verbindungen, XXII. λ3-Phosphazen-Komplexe des nullwertigen Platins
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The reaction of Pt(COD)2 (COD = 1,5-cyclooctadiene) with the λ3-phosphazene RR'N-P=NR, R = (CH3)3C, R' = (CH3)3Si (1), gives the platinum(0) complex PtL3 (2) (L = λ3-phosphazene 1) whose structure has been elucidated by an X-ray analysis. 2 is used for the synthesis of the platinum(0) compounds PtL2L' (L' = R3M, M = P->Sb) (3) and PtLL'2 (L' = R3P) (4).
- Scherer, Otto J.,Konrad, Rainer,Krueger, Carl,Tsay, Yi-Hung
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p. 414 - 426
(2007/10/02)
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