Heterometallic Pt-Au complexes with μ-3 S bridging. Syntheses and structures of Pt2 (PPh3)4(μ-SAuCl)2·2CH2Cl2 and Pt2(PPh3)4−(μ-S)(μ-SAuPPh3)NO3·0.5H2O

Bos, William G.; Bour, J. J.; Schlebos, P. P. J.; Hageman, P.R.; Bosman, W. P.; Smits, J.M.; Wietmarschen, J. A. C. Van; Beurskens, Paul T.

doi:10.1016/s0020-1693(00)84333-9

Cited by 46 publications

(8 citation statements)

References 15 publications

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“…Thus, the different species are labeled with the same number as the parent compound but with an additional t. Their main geometric parameters are collected in Table . The calculated structures agree with the analogous products structurally characterized in this work and with other related complexes reported in the literature. 7b,− …”

Section: Resultssupporting

confidence: 88%

Diverse Evolution of [{Ph₂P(CH₂)_nPPh₂}Pt(μ-S)₂Pt{Ph₂P(CH₂)_nPPh₂}] (n = 2, 3) Metalloligands in CH₂Cl₂

et al. 2002

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The nucleophilicity of the [Pt(2)S(2)] core in [[Ph(2)P(CH(2))(n)PPh(2)]Pt(mu-S)(2)Pt[Ph(2)P(CH(2))(n)PPh(2)]] (n = 3, dppp (1); n = 2, dppe (2)) metalloligands toward the CH(2)Cl(2) solvent has been thoroughly studied. Complex 1, which has been obtained and characterized by X-ray diffraction, is structurally related to 2 and consists of dinuclear molecules with a hinged [Pt(2)S(2)] central ring. The reaction of 1 and 2 with CH(2)Cl(2) has been followed by means of (31)P, (1)H, and (13)C NMR, electrospray ionization mass spectrometry, and X-ray data. Although both reactions proceed at different rates, the first steps are common and lead to a mixture of the corresponding mononuclear complexes [Pt[Ph(2)P(CH(2))(n)PPh(2)](S(2)CH(2))], n = 3 (7), 2 (8), and [Pt[Ph(2)P(CH(2))(n)PPh(2)]Cl(2)], n = 3 (9), 2 (10). Theoretical calculations give support to the proposed pathway for the disintegration process of the [Pt(2)S(2)] ring. Only in the case of 1, the reaction proceeds further yielding [Pt(2)(dppp)(2)[mu-(SCH(2)SCH(2)S)-S,S']]Cl(2) (11). To confirm the sequence of the reactions leading from 1 and 2 to the final products 9 and 11 or 8 and 10, respectively, complexes 7, 8, and 11 have been synthesized and structurally characterized. Additional experiments have allowed elucidation of the reaction mechanism involved from 7 to 11, and thus, the origin of the CH(2) groups that participate in the expansion of the (SCH(2)S)(2-) ligand in 7 to afford the bridging (SCH(2)SCH(2)S)(2-) ligand in 11 has been established. The X-ray structure of 11 is totally unprecedented and consists of a hinged [(dppp)Pt(mu-S)(2)Pt(dppp)] core capped by a CH(2)SCH(2) fragment.

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Section: Resultssupporting

confidence: 88%

Diverse Evolution of [{Ph₂P(CH₂)_nPPh₂}Pt(μ-S)₂Pt{Ph₂P(CH₂)_nPPh₂}] (n = 2, 3) Metalloligands in CH₂Cl₂

et al. 2002

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“…There are approximately 70 examples of derivatives of (Ph 3 P) 4 Pt 2 S 2 in the Cambridge Crystallographic Database (May 2006 version), most of these having the equivalent dihedral angle in the range 123-147°with a mean value of 134°(excluding the parent complex with an angle of 168° [24], and two unusual examples with two AuCl or AgCl groups attached to the S atoms, with angles of 180° [25]). However there does not seem to be any particular pattern to variations in this fold-angle in terms of the number or type of groups attached to the sulfur atom(s), so it appears it is a flexible parameter determined by intramolecular and crystal packing interactions and is not a consequence in 2 and 3 of differing Pb coordination.…”

Section: Resultsmentioning

confidence: 99%

Tuning the sulfur–heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]

Pham¹,

Henderson²,

Nicholson³

et al. 2007

Journal of Organometallic Chemistry

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Reactions of [Pt 2 (l-S) 2 (PPh 3 ) 4 ] with Ph 3 PbCl, Ph 2 PbI 2 , Ph 2 PbBr 2 and Me 3 PbOAc result in the formation of bright yellow to orange solutions containing the cations [Pt 2 (l-S) 2 (PPh 3 ) 4 PbR 3 ] + (R 3 = Ph 3 , Ph 2 I, Ph 2 Br, Me 3 ) isolated as PF 6 À or BPh 4 À salts. In the case of the Me 3 Pb and Et 3 Pb systems, a prolonged reaction time results in formation of the alkylated species [Pt 2 (l-S)(l-SR)(PPh 3 ) 4 ] + (R = Me, Et). X-ray structure determinations on [Pt 2 (l-S) 2 (PPh 3 ) 4 PbMe 3 ]PF 6 and [Pt 2 (l-S) 2 (PPh 3 ) 4 PbPh 2 I]PF 6 have been carried out, revealing different coordination modes. In the Me 3 Pb complex, the (four-coordinate) lead atom binds to a single sulfur atom, while in the Ph 2 PbI adduct coordination of both sulfurs results in a five-coordinate lead centre. These differences are related to the electron density on the lead centre, and indicate that the interaction of the heterometal centre with the {Pt 2 S 2 } metalloligand core can be tuned by variation of the heteroatom substituents. The species [Pt 2 (l-S) 2 (PPh 3 ) 4 PbR 3 ] + display differing fragmentation pathways in their ESI mass spectra, following initial loss of PPh 3 in all cases; for R = Ph, loss of PbPh 2 occurs, yielding [Pt 2 (l-S) 2 (PPh 3 ) 3 Ph] + , while for R = Me, reductive elimination of ethane gives [Pt 2 (l-S) 2 (PPh 3 ) 3 PbMe] + , which is followed by loss of CH 4 .

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“…Among the {Pt 2 S 2 M} aggregates reported, both “Y-shaped”, for example, [Pt 2 (PPh 3 ) 4 ( μ 3 -S) 2 Cu(PPh 3 )]PF 6 [∠P(3)−Cu(3)−S(1) = 135.7(2)° and ∠P(3)−Cu(3)−S(2) = 139.4(4)°], and T-shaped complexes, for example, [Pt 2 (PPh 3 ) 4 ( μ 3 -S)( μ 2 -S)HgPh]BPh 4 11a [∠C(1)−Hg−S(1) = 113.00(15)° and ∠C(1)−Hg−S(2) = 174.59(16)°] have been identified. Another interesting feature of 1 is the significant disparity between the two Hg···Pt distances (3.067 and 3.340 Å), which is not observed in the isoelectronic gold(I) complexes such as [Pt 2 (PPh 3 ) 4 ( μ 3 -S) 2 (AuCl) 2 ] [3.111(1) and 3.218(1) Å] and [Pt 2 (PPh 3 ) 4 ( μ 3 -S)( μ 2 -S)Au(PPh 3 )] + [3.314(1) and 3.231(1) Å] . The dihedral angle ( θ ) of the{Pt 2 S 2 } butterfly core along the S(1)···S(2) axis is 147.4°.…”

Section: Resultsmentioning

confidence: 99%

Synthetic, Structural, Electrochemical, and Theoretical Studies of Heterometallic Aggregates with a [Pt₂(μ-S)₂M] Core (M = Hg, Au)

Fong

et al. 2002

Inorg. Chem.

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Novel electroactive multimetallic compounds based on the [Pt(2)(mu(2)-S)(2)M] core, viz. [Pt(2)(PPh(3))(4)(mu(3)-S)(2)HgFc]PF(6) (1) [Fc = (eta(5)-C(5)H(4))Fe(eta(5)-C(5)H(5))] and [Pt(2)(PPh(3))(4)(mu(3)-S)(2)Hg(2)Fc'](PF(6))(2) (2) [Fc' = Fe(eta(5)-C(5)H(4))(2)], have been synthesized under the guide of electrospray mass spectrometry. The electrochemistry of these ferrocene funtionalized compounds together with the reported [Pt(2)(PPh(3))(4)(mu(3)-S)(2)HgPPh(3)](PF(6))(2) (3), [Pt(2)(PPh(3))(4)(mu(2)-S)(mu(3)-S)HgPh]PF(6) (4), and [Pt(2)(PPh(3))(4)(mu(2)-S)(mu(3)-S)AuPPh(3)]PF(6) (5) have been investigated using cyclic voltammetry and DFT calculations. These results point to a prominent ligand-based oxidation.

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Heterometallic Pt-Au complexes with μ-3 S bridging. Syntheses and structures of Pt2 (PPh3)4(μ-SAuCl)2·2CH2Cl2 and Pt2(PPh3)4−(μ-S)(μ-SAuPPh3)NO3·0.5H2O

Cited by 46 publications

References 15 publications

Diverse Evolution of [{Ph₂P(CH₂)_nPPh₂}Pt(μ-S)₂Pt{Ph₂P(CH₂)_nPPh₂}] (n = 2, 3) Metalloligands in CH₂Cl₂

Diverse Evolution of [{Ph₂P(CH₂)_nPPh₂}Pt(μ-S)₂Pt{Ph₂P(CH₂)_nPPh₂}] (n = 2, 3) Metalloligands in CH₂Cl₂

Tuning the sulfur–heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]

Synthetic, Structural, Electrochemical, and Theoretical Studies of Heterometallic Aggregates with a [Pt₂(μ-S)₂M] Core (M = Hg, Au)

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Heterometallic Pt-Au complexes with μ-3 S bridging. Syntheses and structures of Pt2 (PPh3)4(μ-SAuCl)2·2CH2Cl2 and Pt2(PPh3)4−(μ-S)(μ-SAuPPh3)NO3·0.5H2O

Cited by 46 publications

References 15 publications

Diverse Evolution of [{Ph2P(CH2)nPPh2}Pt(μ-S)2Pt{Ph2P(CH2)nPPh2}] (n = 2, 3) Metalloligands in CH2Cl2

Diverse Evolution of [{Ph2P(CH2)nPPh2}Pt(μ-S)2Pt{Ph2P(CH2)nPPh2}] (n = 2, 3) Metalloligands in CH2Cl2

Tuning the sulfur–heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]

Synthetic, Structural, Electrochemical, and Theoretical Studies of Heterometallic Aggregates with a [Pt2(μ-S)2M] Core (M = Hg, Au)

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Diverse Evolution of [{Ph₂P(CH₂)_nPPh₂}Pt(μ-S)₂Pt{Ph₂P(CH₂)_nPPh₂}] (n = 2, 3) Metalloligands in CH₂Cl₂

Diverse Evolution of [{Ph₂P(CH₂)_nPPh₂}Pt(μ-S)₂Pt{Ph₂P(CH₂)_nPPh₂}] (n = 2, 3) Metalloligands in CH₂Cl₂

Synthetic, Structural, Electrochemical, and Theoretical Studies of Heterometallic Aggregates with a [Pt₂(μ-S)₂M] Core (M = Hg, Au)