Formation and isomerisation of cis-bis(phenylethynyl)bis(tertiary phosphine)platinum complexes

Cross, Ronald J.; Davidson, Michael F.

doi:10.1039/dt9860001987

Cited by 71 publications

(38 citation statements)

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“…The precursor derivative cis-[Pt(CϵCC 6 H 4 CϵCPh) 2 -(cod)] (1) was obtained using a similar procedure to that used for related cis-[Pt(CϵCR) 2 (cod)] (R = Ph, [56] tBu [57] ) derivatives. Thus, the reaction of an ethanolic suspension of [PtCl 2 (cod)] at low temperature (-30°C) with HCϵCC 6 H 4 CϵCPh (2 equiv.)…”

Section: Resultsmentioning

confidence: 99%

Ethynyltolan Platinum Complexes with (Arylalkynyl)phosphane Ligands

García

Lalinde

2007

Eur J Inorg Chem

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The ethynyltolan mononuclear complexes cis‐[Pt(C≡CC6H4C≡CPh)2(PPh2C≡CR)2] [R = tol (2), C6H4C≡CPh (3)], which contain (arylalkynyl)phosphane ligands, were prepared, and the X‐ray molecular structure of 2 was determined. The reaction of 2 and 3 with cis‐[Pt(C6F5)2(thf)2] (thf = tetrahydrofuran) in the appropriate molar ratio gave the dinuclear platinum derivatives cis‐[{Pt(PPh2C≡CR)2(μ‐η1:η2‐Cα,Cβ‐C≡CC6H4C≡CPh)2}Pt(C6F5)2] [R = tol (4), C6H4C≡CPh (5)] and the trinuclear derivatives [{Pt(μ‐η1:η2‐Cα,Cβ‐C≡CC6H4C≡CPh)2(μ‐1κP:2η2‐Cα,Cβ‐PPh2C≡CR)2}{Pt(C6F5)2}2][R = tol (6), C6H4C≡CPh (7)], which are stabilized by a double ethynyltolan bridging system or a mixed ethynyltolan/alkynylphosphane bridging system, respectively.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Section: Resultsmentioning

confidence: 99%

Ethynyltolan Platinum Complexes with (Arylalkynyl)phosphane Ligands

García

Lalinde

2007

Eur J Inorg Chem

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“…[12a] Ph [14] ), (NBu 4 ) 2 [cis-{Pt(C 6 F 5 ) 2 Cl} 2 (m-dppa)], [16] [M(m-Cl)(cod)] 2 (M = Rh, [25a] Ir [25b] ) and [cis-Pt(C 6 F 5 ) 2 (thf) 2 ] [26] were prepared according to literature methods. All other reagents were used as obtained commercially.…”

Section: Methodsmentioning

confidence: 99%

“…[10] We have shown that neutral cis-or trans-bis(alkynyl)platinum complexes of type [Pt(CCR) 2 L 2 ] [11, 12a] and, particularly, mixed [cis/trans-Pt(C 6 F 5 ) 2 (CCR) 2 ] 2À[9f, 12] and homoleptic [Pt(C CR) 4 ] 2À [9a,b,d, 13] (R = Ph, tBu, SiMe 3 ) anionic species are excellent precursors to the synthesis of polymetallic species stabilized via h 2 -alkyne±metal and in some cases Pt¥¥¥metal bonding interactions. We have also found that anionic platinum substrates are able to act as mono- [12a,d,e, 13a,d] or even dialkynylating [12c,d, 13c] [14] ) with two equivalents of (NBu 4 )CN in acetone (Scheme 1a). This synthetic strategy, previously used by us and others with phosphine ligands, [11b, 12a, 15] caused the displacement of the cyclooctadiene by the cyanide ligands and led to the formation of the dianionic species quantitatively, as observed by NMR spectroscopy.…”

Section: Introductionmentioning

confidence: 92%

Discrete Triangle, Square and Hexametallic Alkynyl Cyano‐Bridged Compounds Based on [cis‐Pt(CCR)₂(CN)₂]²⁻ Building Blocks

Forniés

Gómez

Lalinde

2004

Chemistry A European J

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Novel mixed bis(alkynyl)bis(cyano)platinate(II) species [cis-Pt(Ctbond;CR)(2)(CN)(2)](2-) (1 a: R = tBu, 1 b: R = Ph) have been prepared and their potential as building blocks in the generation of self-organized systems with a variable molecular architecture has been studied. The reaction of 1 with the ditopic acceptor species [[cis-Pt(C(6)F(5))(2)S](2)(dppa)] (dppa=diphenylphosphinoacetylene) gave the dianionic cyanide/dppa bridged molecular platinotriangles (NBu(4))(2)[(C(6)F(5))(2)Pt(micro-dppa)[(micro-CN)(2)Pt(Ctbond;CR)(2)]Pt(C(6)F(5))(2)] (2). X-ray analysis of 2 a confirmed that the "Pt(2)(C(6)F(5))(4)(micro-dppa)" binuclear moiety is connected to the dianionic "Pt(Ctbond;CR)(2)(CN)(2)" unit by two bridging cyanide ligands. Moreover, treatment of 1 with the solvent cationic species [M(cod)(acetone)(2)](+) afforded heterometallic molecular squares Pt(2)M(2) (M=Rh, Ir) containing cyanide bridges and terminal alkynyl ligands, (NBu(4))(2)[cyclo[[cis-Pt(Ctbond;CR)(2)(micro-CN)(2)][M(cod)]](2)] (3: M=Rh, 4: M = Ir). The solid-state structures of phenyl derivatives have been determined by X-ray crystallography. The terminal alkynyl ligands in these cyanide-bridged molecular squares 3 and 4 have been used in the assembly of higher multimetallic complexes. Thus, very unusual bis(double-alkynide)-cyanide-bridged hexametallic compounds (NBu(4))(2)[[(C(6)F(5))(2)Pt(micro-Ctbond;CPh)(2)(micro-CN)(2)](2)[M(cod)](2)] (5 b: M=Rh, 6 b: M = Ir) were easily formed by simple reactions of 3 b and 4 b with two equivalents of [cis-Pt(C(6)F(5))(2)(thf)(2)]. An X-ray diffraction study on complex 5 b indicated that the derivative was formed by a simultaneous migration of one sigma-alkynyl group from each "Pt(Ctbond;CPh)(2)(micro-CN)(2)" corner of the square to both "Pt(C(6)F(5))(2)" units, resulting in bent sigma,pi-double-alkynyl bridging systems. Finally, the novel supramolecular anionic assemblies (NBu(4))(4)[cyclo[[cis-Pt(Ctbond;CR)(2)(micro-CN)(2)][SnPh(3)]](4)] 7 have been obtained by self-assembly of 1 and [SnPh(3)(acetone)(2)](+).

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“…Aldehyde 51 was converted to the 1-(2,2-dibromovinyl) derivative 52. [30] In contrast to 9 (Scheme 2), 51 reacted slowly with Ph 3 P= CBr 2 (prepared in situ), and the highest yield of 52 was achieved by heating a mixture of PPh 3 , CBr 4 , and 51 in CH 2 Cl 2 for 36 h. [46] The 1-ethynyl derivative 53 was obtained in an 78 % yield by reductive dehydrobromination of 52 with NaNH 2 /liquid ammonia without the formation of the vinyl side product. This is to be contrasted with the dehydrochlorination of the 2,2-dichloroethylated para-carborane intermediate, which was accompanied by the formation of the undesirable vinyl compound.…”

Section: Synthesis Of Highly B-methylated M-carborarodsmentioning

confidence: 99%

Camouflaged Carborarods Derived from B‐Permethyl‐1,12‐diethynyl‐para‐ and B‐Octamethyl‐1,7‐diethylnyl‐meta‐carborane Modules

Herzog¹,

Jalisatgi²,

Knobler³

et al. 2005

Chemistry A European J

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Rigid camouflaged carborarods constructed from the corresponding C,C'-diethynyl derivatives of B-decamethyl-1,12-dicarbadodecaborane(12) (6) and B-octamethyl-1,7-dicarbadodecaborane(12) (48) have been synthesized by largely conventional organic transformations. These carborarods are the longest discrete rod species available by this method in which B-methylated p-carborane and m-carborane cages are linked through their carbon vertices by using butadiynylene moieties. They exhibit enhanced solubility in common organic solvents relative to all other presently known carborane-based rigid-rod molecules. The oxidative coupling of bis(ethynyl) derivatives of 6 generates oligomers containing, on average, 16 carborane modules. The structural characterization of the corresponding dimeric species revealed that the carborarods possess a sinusoidal chain distortion in the solid state. The stereoelectronic properties of these and related model carborarods were evaluated by using molecular dimensions as a monitor for the comparison of computational and experimental methods. In addition, the effect of exhaustive B-methylation of 12- and 10-vertex para-carborane cages in a series of model C,C'-diethynyl derivatives was similarly investigated by computational and structural studies. As expected, a correlation of intercage C--C bond lengths with cage size was observed and was attributed to hybridization effects. B-Permethylation had no significant structural effect with either 10- or 12-vertex cage derivatives. Relative to unsubstituted compounds, thermal and chemical stabilities of B-permethylated derivatives were increased through the operation of a steric "bumper-car" process, and solubilities in organic solvents were enhanced. The formation of linear, sterically encumbered platina-carborarods using ethynyl derivatives of 6 as precursors is described.

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Formation and isomerisation of cis-bis(phenylethynyl)bis(tertiary phosphine)platinum complexes

Cited by 71 publications

References 0 publications

Ethynyltolan Platinum Complexes with (Arylalkynyl)phosphane Ligands

Ethynyltolan Platinum Complexes with (Arylalkynyl)phosphane Ligands

Discrete Triangle, Square and Hexametallic Alkynyl Cyano‐Bridged Compounds Based on [cis‐Pt(CCR)₂(CN)₂]²⁻ Building Blocks

Camouflaged Carborarods Derived from B‐Permethyl‐1,12‐diethynyl‐para‐ and B‐Octamethyl‐1,7‐diethylnyl‐meta‐carborane Modules

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Formation and isomerisation of cis-bis(phenylethynyl)bis(tertiary phosphine)platinum complexes

Cited by 71 publications

References 0 publications

Ethynyltolan Platinum Complexes with (Arylalkynyl)phosphane Ligands

Ethynyltolan Platinum Complexes with (Arylalkynyl)phosphane Ligands

Discrete Triangle, Square and Hexametallic Alkynyl Cyano‐Bridged Compounds Based on [cis‐Pt(CCR)2(CN)2]2− Building Blocks

Camouflaged Carborarods Derived from B‐Permethyl‐1,12‐diethynyl‐para‐ and B‐Octamethyl‐1,7‐diethylnyl‐meta‐carborane Modules

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Discrete Triangle, Square and Hexametallic Alkynyl Cyano‐Bridged Compounds Based on [cis‐Pt(CCR)₂(CN)₂]²⁻ Building Blocks