(.mu.-Methylene)diplatinum complexes: their syntheses, structures, and properties

Azam, Kazi A.; Frew, Aileen A.; Lloyd, Brian R.; Manojlović-Muir, Ljubica; Muir, Kenneth W.; Puddephatt, Richard J.

doi:10.1021/om00127a016

Cited by 44 publications

(14 citation statements)

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“…The solid state structures of a number of dipalladium − and diplatinum − A-frame complexes have been reported. A large majority of these adopt elongated boat conformations, the exceptions being the carbonyl-bridged dipalladium species [Pd 2 Cl 2 (μ-CO)(μ-dmpm) 2 ] 19 and [Pd 2 (OCOCF 3 ) 2 (μ-CO)(μ-dppm) 2 ] 23 and [Pt 2 Me 2 (μ-H)(μ-dppm) 2 ]PF 6 , which exist in chair conformations.…”

Section: Resultsmentioning

confidence: 99%

Reactions of [PdX₂(dppm)] Complexes with Grignard Reagents

1997

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Reactions of [PdX2(dppm)] (X = Cl, Br) with a range of Grignard reagents have been investigated. Diorganopalladium complexes of the type [PdR2(dppm)] were obtained in good yield with the bulky mesityl or trimethylsilylmethyl groups, provided the reactions were performed using high Grignard:Pd ratios in ether solution. With the smaller R groups Me, Et, Bu, and CH2Ph, only the halide-bridged A-frame complexes [Pd2R2(μ-X)(μ-dppm)2]+ were formed, irrespective of the reaction conditions. Mixtures of chloride- and bromide-bridged complexes were produced when [PdCl2(dppm)] was treated with RMgBr, so [PdBr2(dppm)] was used as the starting material in certain cases. The mesityl derivative [Pd2(C6H2Me3)2(μ-Br)(μ-dppm)2]+ could be obtained from the reaction of [PdBr2(dppm)] with 4 mol equiv of C6H2Me3MgBr in CH2Cl2 solution, but with Me3SiCH2MgCl mixtures of monomeric and dimeric complexes were obtained under these conditions. The A-frame complex [Pd2(CH2SiMe3)2(μ-Cl)(μ-dppm)2]+ was generated, however, by reaction of [Pd(CH2SiMe3)2(dppm)] with 1 mol equiv of HCl. The A-frames were isolated as their PF6 - salts. They were characterized by elemental analysis, NMR spectroscopy, and, in the case of [Pd2(C6H2Me3)2(μ-Br)(μ-dppm)2]PF6, X-ray crystallography. The molecular structure of the [Pd2(C6H2Me3)2(μ-Br)(μ-dppm)2]+ cation reveals that it adopts an elongated boat conformation, with the dppm CH2 groups lying on the same side of the Pd2P4 framework as the bridging bromide. With the smaller aryl Grignards PhMgBr, p-tolylMgBr, or o-tolylMgCl, the diarylpalladium species [PdAr2(dppm)] could be detected in solution at low temperatures but at ambient temperature reductive coupling of the aryl groups occurred and the palladium(I) complexes [Pd2X2(μ-dppm)2] were formed.

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Section: Resultsmentioning

confidence: 99%

Reactions of [PdX₂(dppm)] Complexes with Grignard Reagents

1997

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“…The Pt-Pt separation of 3.0962(4) Å, indicating the absence of a Pt-Pt bond, is shorter than those for the A-frame diplatinum complexes with dppm ligands, e.g. 8 and is comparable to that of [Pt 2 Cl 2 (m-CS 2 )(mdppm) 2 ] (3.094 Å). 9 Two nitrosyl groups are inserted into the two Pt-Pt bonds of 2a with an almost symmetrical manner, Pt1-N1 2.020(6) Å, Pt2-N1 2.019(6) Å, Pt1-N1-Pt2 100.1(3)°, Pt1-N1-O1 125.9(6)°, Pt2-N1-O1 133.2(6)°, resulted in a double-A-frame trimetallic structure.…”

mentioning

confidence: 78%

“…This nitrosyl-bridging structure is quite different from that of 3 which involves an NO 2 unit with an N-O bond length of 1.20(2) Å. 7,8 From the X-ray crystal structure, the present reaction can be regarded as a novel three-center oxidative addition proceeding on a linear triplatinum center, which involves an apparent two electron transfer from the triplatinum core to two NO + ions.…”

mentioning

confidence: 87%

Unprecedented nitrosyl-bridged double-A-frame triplatinum complexes, [Pt3(μ-triphosphine)2(μ-NO)2(RNC)2](BF4)4

Tanase¹,

Hamaguchi²,

Begum³

et al. 1999

Chem. Commun.

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“…An immediate reaction occurred and metallic gold was precipitated. After 10 min, the solution was filtered, the solvents evaporated, and the product was identified as [Pt2C12(p-CH2)(p-dppm)2] by its 'H and 3 1~ NMR spectra (25).…”

Section: Reaction Of 5 With Chzn2mentioning

confidence: 99%

A route to trinuclear platinum–gold clusters

Arsenault¹,

Puddephatt²

1989

Can. J. Chem.

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Gillespie on the occasion of his 65th birthday G. J. ARSENAULT and R. J. PUDDEPHATT. Can. J. Chem. 67, 1800 (1989). New A-frame cluster complexes have been prepared by addition of electrophilic gold fragments to the Pt-Pt bond of Heteronuclear cluster compounds containing the coinage metals are currently attracting considerable interest (1-9) and now constitute a well-established class of compounds, especially when the coinage metal is gold. However, relatively few reports have appeared on mixed-metal cluster complexes containing platinum and one of the coinage metals (4, 5).The reactivity of the metal-metal bond of [Pt2C12(pdppm)2], l a , to insertion reactions with small organic molecules and to addition of electrophilic reagents has been studied (6). These reactions often give "A-frame" complexes, such as [Pt2C12(pCHz)(~-dppm)2] by reaction with CH2N2 and [Pt2Cl2(~-H)(pd~p m )~] + by reaction with H+. However, there has been less work on the reactions of 1 with metal moieties that are isolobal to CH2 or H+. SnC12 does not add to the Pt-Pt bond but inserts into the Pt-C1 bond to give [Pt2C1(SnC13)(pdppm)2] (7). Reaction with the nucleophilic metal carbonyl anion [F~(co)~]'-disrupts the skeleton of 1 to give a triangulo-Pt2Fe complex (8) and other carbonylmetallates may behave similarly. Thus, prior to the initiation of this work (1 1) no A-frame cluster complexes had been synthesized directly by addition of a metal fragment to the Pt-Pt bond of l a . Such complexes appear to have good stability since two examples, 2 (9) and 3 (lo), have been prepared indirectly, and the complex [Pt2Cl2(pHgCl2)(~-d p~m )~] was prepared recently by direct addition of HgC12 to l a (12).Herein, we report the reactions of complexes 1 with several electrophilic gold fragments that are isolobal with H+. Complex l a gives A-frame complexes containing Pt2Au units by addition '~u t h o r to whom correspondence may be addressed.of the gold moeity across the Pt-Pt bond of l a . However, l b and l c fail to give the corresponding A-frame complexes containing Pd2Au or PdPtAu units. Reaction of l a with similar copper or silver fragments also does not give A-frame complexes. Results and discussion Synthesis and characterization of PtzAu A-frame complexesThe reaction of equimolar amounts of l a and [Au(N03)(PPh3)] Can. J. Chem. Downloaded from www.nrcresearchpress.com by 34.215.51.103 on 05/12/18For personal use only.

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(.mu.-Methylene)diplatinum complexes: their syntheses, structures, and properties

Cited by 44 publications

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Reactions of [PdX₂(dppm)] Complexes with Grignard Reagents

Reactions of [PdX₂(dppm)] Complexes with Grignard Reagents

Unprecedented nitrosyl-bridged double-A-frame triplatinum complexes, [Pt3(μ-triphosphine)2(μ-NO)2(RNC)2](BF4)4

A route to trinuclear platinum–gold clusters

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(.mu.-Methylene)diplatinum complexes: their syntheses, structures, and properties

Cited by 44 publications

References 0 publications

Reactions of [PdX2(dppm)] Complexes with Grignard Reagents

Reactions of [PdX2(dppm)] Complexes with Grignard Reagents

Unprecedented nitrosyl-bridged double-A-frame triplatinum complexes, [Pt3(μ-triphosphine)2(μ-NO)2(RNC)2](BF4)4

A route to trinuclear platinum–gold clusters

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Reactions of [PdX₂(dppm)] Complexes with Grignard Reagents

Reactions of [PdX₂(dppm)] Complexes with Grignard Reagents