Regioselective Dimetallapolycarbyl Hydrometalation

Dewhurst, Rian D.; Hill, Anthony F.; Smith, Matthew K.

doi:10.1021/om050796g

Cited by 11 publications

(4 citation statements)

References 14 publications

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“…Due to the established oxidative addition reactions of 1 to ruthenium(0), rhodium(I) (inferred but not directly observed in the catalytic demercuration of 1 ), and iridium(I) d 8 -metal complexes and their curious reactions with [PtCl 2 (PPh 3 ) 2 ], we wished to investigate the reactivity of these mercurials toward Pt(0) complexes. We had hoped that, unlike those of Pt(II), products of oxidative addition to Pt(0) would be stable, isolable complexes in the absence of mercuric chloride.…”

Section: Resultsmentioning

confidence: 99%

“…Under the same conditions Vaska’s complex affords the hydridobis(tricarbido) complex [IrH{CCCW(CO) 2 (Tp*)} 2 (CO)(PPh 3 ) 2 ], this being the product of both halide metathesis and C−H oxidative addition . This, unpredictability, coupled with the incompatibility of some transition metal substrates with either moisture or fluoride prompted us to investigate anhydrous tricarbidos of mercury and gold and their reactivity toward d 8 -metal complexes of groups 8 , and 9 . A dichotomy has arisen between the relative stability of the resulting bis(tricarbido) complexes ( A , Chart ) and the reductive elimination partner involving either coordinated ( B ) or free dimetallaoctatetrayne [(Tp*)(CO) 2 WCCCCCCW(CO) 2 (Tp*)] ( 1 ) ( C , Chart ).…”

Section: Introductionmentioning

confidence: 99%

“…1a Under the same conditions Vaska's complex affords the hydridobis(tricarbido) complex [IrH-{CtCCtW(CO) 2 (Tp*)} 2 (CO)(PPh 3 ) 2 ], this being the product of both halide metathesis and C-H oxidative addition. 3 This, unpredictability, coupled with the incompatibility of some transition metal substrates with either moisture or fluoride prompted us to investigate anhydrous tricarbidos of mercury 4 and gold 5 and their reactivity toward d 8 -metal complexes of groups 8 6,7 and 9. (2) to afford 1, 8a while the reaction of 1 with [Ru(CO) 2 (PPh 3 ) 3 ] demonstrates the reverse reaction, in which a C-C bond of the C 6 spine is oxidatively cleaved.…”

Section: Introductionmentioning

confidence: 99%

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The Interplay of Bis(tricarbido) and Dimetallaoctatetrayne Complexes of Platinum

2009

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Non-interconvertible platinum bis(tricarbidotungsten) and dimetallaoctatetrayne π-complexes arise from the reactions of bis(tricarbidotungsten)mercurials and aurates with complexes of platinum(0) and platinum(II). Thus [PtCl 2 (PPh 3 ) 2 ] with either [Hg{C 3 W(CO) 2 (Tp*)} 2 ] or PPN[Au-{C 3 W(CO) 2 (Tp*)}] (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) affords both cis-[Pt{C 3 W-(CO) 2 (Tp*)} 2 (PPh 3 ) 2 ] and [(Tp*)(CO) 2 WC 6 W(CO) 2 (Tp*)], while the latter with [Pt(C 2 H 4 )(PPh 3 ) 2 ] affords the π-complex [Pt{η 2 -(Tp*)(CO) 2 WC 6 W(CO) 2 (Tp*)}(PPh 3 ) 2 ], which does not convert to the bis(tricarbido) isomer. Although an intermediate bis(tricarbidotungsten) complex [Pt{C 3 W(CO) 2 -(Tp*)} 2 (dppe)] (dppe = 1,2-bis(diphenylphosphine)ethane) may be spectroscopically observed to form in the related reaction employing [PtCl 2 (dppe)], this is unstable, ultimately and exclusively evolving to the free dimetallaoctatetrayne. The reaction of [Pt(C 2 H 4 )(PPh 3 ) 2 ] with [Hg{C 3 W(CO) 2 -(Tp*)} 2 ] provides a ca 3:2 mixture of cis-[Pt{C 3 W(CO) 2 (Tp*)} 2 (PPh 3 ) 2 ] and [Pt{η 2 -(Tp*)(CO) 2 WC 6 -W(CO) 2 (Tp*)}(PPh 3 ) 2 ] in addition to traces of [(Tp*)(CO) 2 WC 6 W(CO) 2 (Tp*)]. Circumstantial evidence is presented to suggest that the mercuric chloride liberated in the transmetalation reaction plays a role in subsequent transformations.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The Interplay of Bis(tricarbido) and Dimetallaoctatetrayne Complexes of Platinum

2009

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“…The reactivity of 1 with a small number of metal complexes was previously explored (Scheme 1): reaction with [Pt(h 2 -C2H4)(PPh3)2] furnishes a p-complex where 'Pt(PPh3)2' coordinates to one C≡C bond, 10 regioselective hydrometallation of a C≡C bond occurs with [RuHCl(CO)(PPh3)3], 11 and finally reaction with [Ru(CO)2(PPh3)3] induces scission of the central C-C single bond to ultimately furnish a bis(tricarbido)ruthenium complex [Ru{C≡CC≡W(CO)2(Tp*)}2(CO)2(PPh3)2]. 12 Coordination to the metal-carbon bond was not observed in these reactions although this feature has been utilized extensively in the preparation of transition metal alkylidynes bridging two or more metal centres.…”

Section: Introductionmentioning

confidence: 99%