Metallaborane chemistry. Part III. Oxidative-insertion reactions of eleven-atom monocarbon carbaborane species with zerovalent nickel, palladium, and platinum complexes; the molecular and crystal structure of 1,1 -bis(t-butyl isocyanide)-2-(trimethylamine)-2-carba-1-pallada-closo-decaborane(10)

Carroll, W. Eamon; Green, Michael; Stone, F. Gordon A.; Welch, Alan J.

doi:10.1039/dt9750002263

Cited by 43 publications

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“…The Pd−C(sp) distance of 1.928(11) Å falls within the range of reported bond lengths for a variety of palladium complexes containing isonitriles, e.g. 1.909(16) Å in [(μ-anilino)Pd(C 6 F 5 )( tert -butylNC)] 2 , 1.925(5) Å in PdCl 2 ( tert -butylNC)(diphenyl(2-pyridyl)phosphine), 1.885(7) and 1.935(7) Å in [(μ-1,8-diisocyano- p -menthane)Pd(Br)Cl] 2 , and 2.027(6) Å in 1,1-( tert -butylNC) 2 -2-(NCH 3 ) 3 -2-carba-1-pallada- closo -decaborane . The other features of the isonitrile show no anomalies; thus, a normal triple bond is observed and the isonitrile is almost linear.…”

Section: Resultssupporting

confidence: 74%

Stereospecific Reaction of Molecular Halogens with Palladacyclopentadienes Containing Bidentate Nitrogen Ligands To Give 1,4-Dihalo-1,3-dienes via Palladium(IV) Intermediates

Belzen¹,

Elsevier²,

Dedieu

et al. 2003

Organometallics

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A synthetic and computational study concerning the reactivity of palladacyclopentadienes containing bidentate nitrogen ligands toward dihalogens is described. The complexes 2,3,4,5-tetrakis(carbomethoxy)palladacyclopentadiene(NN) (1a-c; NN ) 9,10-bis(phenylimino)-9,-10-dihydrophenanthrene (phenyl-bip, a), bis(p-tolylimino)acenaphthene ((p-tolyl)-bian, b), 2,2′-bipyridine (bpy, c)) reacted with molecular dihalogens to give (E,E)-1,4-dihalo-1,2,3,4-tetrakis(carbomethoxy)-1,3-butadiene and PdX 2 (NN) (X ) Cl, Br, I). The palladacycles 1a,b react at 203-208 K with bromine to give the palladium(IV) species trans,cis,cis-(E,E)-2,3,4,5-tetrakis(carbomethoxy)palladacyclopentadiene dibromide(NN) (3av and 3bv, respectively), which were observed by low-temperature 1 H NMR. Above 243 K reductive elimination took place and the divalent compounds (E,E)-{1,2,3,4-tetrakis(carbomethoxy)-4-halo-1,3-butadienyl}-palladium(II) bromide(NN) (4av and 4bv) were cleanly obtained. Similar (σ-1,3-dienyl)-palladium halide complexes 4au-4cw were prepared by reacting the palladacycles 1a-c with a stoichiometric amount of chlorine, bromine, or iodine. The energy profile obtained from DFT-B3LYP calculations, which have been carried out using [(HNCHCHNH)Pd(C 4 -(CN) 4 )] + Br 2 as a model system, show that this sequence of oxidative addition of molecular halogen to the palladacyclic compound, generating a Pd(IV) species, followed by reductive elimination with formation of a carbon-halogen bond is energetically feasible. The calculations also point to the possible involvement of a Pd(Br 2 ) complex in the early stages of the reaction. Palladacycles 6 derived from hexafluorobutyne (E ) CF 3 ) reacted analogously, to give (E,Z)-{1,2,3,4-tetrakis(trifluoromethyl-4-halo-1,3-butadienyl}palladium(II) halide(NN) compounds 7u-w after E,Z isomerization of the ∆(3,4) alkene bond. When the (σ-1,3-dienyl)-palladium halides 4au-4cw were reacted with an additional 1 equiv of another dihalogen, Y 2 , it was found that an unsymmetric diene, (E,E)-{1-X,4-Y}-1,2,3,4-tetrakis(carbomethoxy)-1,3-butadiene, was selectively formed, indicating that the intermediate Pd(IV) complex stereospecifically eliminates the (entering) apical halogen Y and the dienyl fragment. Finally, several ionic compounds 10bz, 11bz, and 11bz′ were obtained by addition of silver triflate to solutions of 4bz in the presence of a noncoordinating solvent or isonitriles, respectively. The X-ray crystal structures of [1,2,3,4-tetrakis(carbomethoxy)-4-iodo-1,3-butadienylpalladium(II) iodide(σ 2 N,N′-2,2′-bipyridyl)] (4cw) and of [1,2,3,4-tetrakis(carbomethoxy)-1,3-pentadienylpalladium(II)(tert-butyl isocyanide)(σ 2 N,N′-p-tolyl-bian)] trifluoromethanesulfonate (11bz) have been determined by X-ray diffraction.

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Section: Resultssupporting

confidence: 74%

Stereospecific Reaction of Molecular Halogens with Palladacyclopentadienes Containing Bidentate Nitrogen Ligands To Give 1,4-Dihalo-1,3-dienes via Palladium(IV) Intermediates

Belzen¹,

Elsevier²,

Dedieu

et al. 2003

Organometallics

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“…Gordon Stone and his co-workers at the University of Bristol pioneered an extensive and interesting chemistry of platinacarbaboranes, reporting families of new compounds such as [(PR 3 ) 2 PtC 2 R 2 B 4 H 4 ], [(PR 3 ) 2 PtC 2 R 2 B 5 H 5 ], [(PR 3 ) 2 PtC 2 R 2 B 6 H 6 ], [(PR 3 ) 2 PtC 2 R 2 B 7 H 9 ], [(PR 3 ) 2 PtC 2 B 8 H 10 ], [(PR 3 )HPtC 2 B 8 H 11 ], [(PR 3 ) 2 PtC 2 R 2 B 9 H 9 ], [(PR 3 ) 2 PtB 10 H 10 C(NMe 3 )], and [(PPh 3 )HPtCB 10 H 11 ] . This interesting new chemistry acted as inspiration and encouragement for many groups throughout the world.…”

Section: Introductionmentioning

confidence: 99%

Polyhedral Platinaborane Chemistry. Interaction of PMe₂Ph with [(PMe₂Ph)₂PtB₁₀H₁₂]

2011

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In solution, [(PMe 2 Ph) 2 PtB 10 H 12 ] (1) and PMe 2 Ph exist in dynamic equilibrium with [(PMe 2 Ph) 3 PtB 10 H 12 ] (2). The activation energy for the dynamic process, ΔG ⧧ , is ca. 63 kJ mol −1 at +17 °C, with ΔS being ca. 335 J mol −1 deg −1 and ΔH ca. 105 kJ mol −1 for the equilibrium. At low temperatures a rocking fluxionality of the {Pt(PMe 2 Ph) 3 } unit versus the {η 4 -B 10 H 12 } unit in 2 becomes apparent, with an activation energy ΔG ⧧ of ca. 28 kJ mol −1 at ca. −105 °C. Compound 2 is characterized by NMR spectroscopy and by a single-crystal X-ray diffraction analysis, for which the results suggest that, in contrast to the common view, the extra electron pair gained by the metal-atom center in going from 1 to 2 does not disrupt the cluster electron count proper nor the observed nido electronic structure and geometry.

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“…Thus, whereas several platinacarborane complexes with closo -PtC 2 B 9 cage frameworks have been well characterized, − as far as we are aware there are only two known monocarbon carborane−platinum compounds with closo -icosahedral structures: [NMe 4 ][Pt(PEt 3 ) 2 (η 5 -7-CB 10 H 11 )] and [Pt(PEt 3 ) 2 (η 5 -7-NMe 3 -7-CB 10 H 10 )]. Both complexes were synthesized by polyhedral expansion reactions involving treatment of [NMe 4 ][ closo -CB 10 H 11 ] and closo -7-NMe 3 -CB 10 H 10 , respectively, with [Pt(PEt 3 ) 2 ( trans -PhC(H)C(H)Ph)] …”

Section: Introductionmentioning

confidence: 99%

Synthesis of the Reagent [Na][Pt(PEt₃)₂(η⁵-7-CB₁₀H₁₁)] and Preparation of the Platinacarborane Complexes [PtX(PEt₃)₂(η⁵-7-CB₁₀H₁₁)] (X = H, Au(PPh₃), Cu(PPh₃), HgPh)

et al. 1997

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The salt [Na][Pt(PEt3)2(η5-7-CB10H11)] (1a) has been prepared. Protonation affords the hydrido complex [PtH(PEt3)2(η5-7-CB10H11)] (2) while reactions with [AuCl(PPh3)], [CuCl(PPh3)]4, and [HgClPh] yield the dimetal compounds [PtM(PEt3)2(PPh3)(η5-7-CB10H11)] (3a, M = Au; 3b, M = Cu) and [PtHgPh(PEt3)2(η5-7-CB10H11)] (3c), respectively. The salt [N(PPh3)2][Pt(CO)(PPh3)(η5-7-CB10H11)] (4) has also been obtained. Single-crystal X-ray diffraction studies have been made on 2 and 3a−c. Complexes 2, 3a, and 3c have similar molecular structures with H, Au(PPh3), and HgPh groups, respectively, σ-bonded to the Pt of the Pt(PEt3)2(η5-7-CB10H11) group. In 3b, however, the copper atom of the Cu(PPh3) moiety is attached to the Pt(PEt3)2(η5-7-CB10H11) fragment both by a Pt−Cu σ-bond and by two exopolyhedral B−H⇀Cu donor bonds from BH groups in the open face of the nido-7-CB10H11 cage ligating the platinum. The structure of the salt 4 has also been determined by X-ray diffraction.

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Metallaborane chemistry. Part III. Oxidative-insertion reactions of eleven-atom monocarbon carbaborane species with zerovalent nickel, palladium, and platinum complexes; the molecular and crystal structure of 1,1 -bis(t-butyl isocyanide)-2-(trimethylamine)-2-carba-1-pallada-closo-decaborane(10)

Cited by 43 publications

References 0 publications

Stereospecific Reaction of Molecular Halogens with Palladacyclopentadienes Containing Bidentate Nitrogen Ligands To Give 1,4-Dihalo-1,3-dienes via Palladium(IV) Intermediates

Stereospecific Reaction of Molecular Halogens with Palladacyclopentadienes Containing Bidentate Nitrogen Ligands To Give 1,4-Dihalo-1,3-dienes via Palladium(IV) Intermediates

Polyhedral Platinaborane Chemistry. Interaction of PMe₂Ph with [(PMe₂Ph)₂PtB₁₀H₁₂]

Synthesis of the Reagent [Na][Pt(PEt₃)₂(η⁵-7-CB₁₀H₁₁)] and Preparation of the Platinacarborane Complexes [PtX(PEt₃)₂(η⁵-7-CB₁₀H₁₁)] (X = H, Au(PPh₃), Cu(PPh₃), HgPh)

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Metallaborane chemistry. Part III. Oxidative-insertion reactions of eleven-atom monocarbon carbaborane species with zerovalent nickel, palladium, and platinum complexes; the molecular and crystal structure of 1,1 -bis(t-butyl isocyanide)-2-(trimethylamine)-2-carba-1-pallada-closo-decaborane(10)

Cited by 43 publications

References 0 publications

Stereospecific Reaction of Molecular Halogens with Palladacyclopentadienes Containing Bidentate Nitrogen Ligands To Give 1,4-Dihalo-1,3-dienes via Palladium(IV) Intermediates

Stereospecific Reaction of Molecular Halogens with Palladacyclopentadienes Containing Bidentate Nitrogen Ligands To Give 1,4-Dihalo-1,3-dienes via Palladium(IV) Intermediates

Polyhedral Platinaborane Chemistry. Interaction of PMe2Ph with [(PMe2Ph)2PtB10H12]

Synthesis of the Reagent [Na][Pt(PEt3)2(η5-7-CB10H11)] and Preparation of the Platinacarborane Complexes [PtX(PEt3)2(η5-7-CB10H11)] (X = H, Au(PPh3), Cu(PPh3), HgPh)

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Polyhedral Platinaborane Chemistry. Interaction of PMe₂Ph with [(PMe₂Ph)₂PtB₁₀H₁₂]

Synthesis of the Reagent [Na][Pt(PEt₃)₂(η⁵-7-CB₁₀H₁₁)] and Preparation of the Platinacarborane Complexes [PtX(PEt₃)₂(η⁵-7-CB₁₀H₁₁)] (X = H, Au(PPh₃), Cu(PPh₃), HgPh)