Synthesis and Characterization of [OsCl2(=C=CHR)(PPh3)2] and Related Complexes

Wen, Ting Bin; Hung, WaiYiu; Zhou, Zhóngyuan; Lo, Man Fung; Williams, Ian D.; Jia, Guochen

doi:10.1002/ejic.200400003

Cited by 28 publications

(23 citation statements)

References 73 publications

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“…As confirmed by single-crystal X-ray diffraction analysis, it contains an essentially planar metallanaphthalyne unit ( Figure 3). [16,18] The Os À C5 bond length (2.127 (3) ) is within the range of those observed for typical OsÀC(aryl) bonds (1.98-2.28 ) [16,19] and at the high end of typical Os=C(carbene) bonds (1.78-2.14 ). The OsÀC1 bond length (1.732 (4) ) is within the range of those observed for typical OsC bonds (1.69-1.79 ) [16,17] and is significantly smaller than those found for typical vinylidene complexes Os = C = CRR' (1.78-1.90 ).…”

supporting

confidence: 64%

“…The OsÀC1 bond length (1.732(4) ) is within the range of those observed for typical OsC bonds (1.69-1.79 ) [16,17] and is significantly smaller than those found for typical vinylidene complexes Os = C = CRR' (1.78-1.90 ). [16,18] The Os À C5 bond length (2.127 (3) ) is within the range of those observed for typical OsÀC(aryl) bonds (1.98-2.28 ) [16,19] and at the high end of typical Os=C(carbene) bonds (1.78-2.14 ). [16,20] Despite the large difference in the OsÀC bond lengths, no simple CÀC bond-distance alternation was observed for the metallacycle, as would be implied from the canonical form drawn in Scheme 2.…”

supporting

confidence: 53%

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A Metallanaphthalyne Complex from Zinc Reduction of a Vinylcarbyne Complex

Zhu

Hung

et al. 2007

Angewandte Chemie

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Transition metal containing metallaaromatics are a fascinating class of compounds because they can show properties of both organometallic compounds and aromatic organic compounds.[1] The most common metallaaromatics are metallabenzenes, stable examples of which have been found for osmium, [2] iridium, [3] platinum, [4] and ruthenium. [5] Other interesting metallaaromatics and related compounds isolated in recent years include metallanaphthalene, [6] metallapyrylium, [7] metallathiabenzene, [8] metallapyridine, [9] metallabenzyne, [10] isometallabenzene, [11] and metallabenzvalene.[12]Here we report the synthesis and characterization of the first metallanaphthalyne.Compared to metallabenzenes, the chemistry of metallabenzynes is less developed, partly due to the lack of convenient methods to construct the metallabenzyne ring. In a search for new routes to metallabenzynes, we tried to reduce the carbyne complex [OsCl 3 (CCH=CPh 2 )(PPh 3 ) 2 ] (1) with zinc.[13] We envisaged that Zn might first reduce the carbyne complex to the 16 e species [OsCl( CCH = CPh 2 )(PPh 3 ) 2 ], which could undergo C À H oxidative addition to give an osmanaphthalyne. Treatment of 1 with zinc powder in THF heated at reflux for 1.5 h produced the indenyl complex [{h 5 -C 9 H 6 (Ph)}OsCl(PPh 3 ) 2 ] (2), along with other unidentified species. Complex 2 can be isolated in 39 % yield from the reaction. The reaction is cleaner in the presence of PPh 3 . In this case, complex 2 can be isolated as a red solid in 71 % yield [Eq. (1)].

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confidence: 64%

supporting

confidence: 53%

A Metallanaphthalyne Complex from Zinc Reduction of a Vinylcarbyne Complex

Zhu

Hung

et al. 2007

Angewandte Chemie

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“…[18] The smallest corner-center-corner angle of the octahedron is found for P-Os-O (80.0(1)°], which is probably due to the ring strain in the five-membered OsPC 2 O chelating system.…”

Section: Resultsmentioning

confidence: 97%

Osmium(II) and Osmium(IV) Complexes with Phosphane–Ethers, –Esters, and –Amines as Mono‐ and Bidentate Ligands

Weber

Werner

2007

Eur J Inorg Chem

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, 8), which were also obtained on heating the osmium(IV) precursor 3 or the labile 1:1 adducts of 3 and 4 with ethene in benzene under reflux. The dihydrido compounds 2 and 3 reacted with CO at room temperature to give initially the octahedral all-cis-configured complexes [OsCl 2 (CO) 2 {κ(P)-iPr 2 PCH 2 CH 2 OMe} 2 ] (11a) and [OsCl 2 (CO) 2 {κ(P)-iPr 2 PCH 2 CO 2 Me} 2 ] (12a), which rearrange to the more stable cis,cis,trans isomers 11b and 12b in benzene under reflux. The all-trans isomer 11c and the monocarbonyl complexes trans,trans-[OsCl 2 (CO){κ 2 (P,O)-

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“…Similarly, when 2 reacted with HC CCH(OH)CH = CH 2 or HC CCH(OH)CH 2 CH 3 under the same reaction conditions, the other two iso-osmabenzenes, 4 (88 % yield) and 5 (80 % yield), were also formed (Scheme 2).The structure of 3 was characterized by single-crystal X-ray diffraction analysis. [10] As shown in Figure 1, the sixmembered ring is almost planar. The deviations, in , from the best plane are 0.0410 (Os1), 0.0003 (C1), 0.0515 (C2), 0.0571 (C3), 0.0022 (C4), and 0.0491 (C5).…”

mentioning

confidence: 91%

“…The structure of 3 was characterized by single-crystal X-ray diffraction analysis. [10] As shown in Figure 1, the sixmembered ring is almost planar. The deviations, in , from the best plane are 0.0410 (Os1), 0.0003 (C1), 0.0515 (C2), 0.0571 (C3), 0.0022 (C4), and 0.0491 (C5).…”

mentioning

confidence: 91%

Stable Iso‐osmabenzenes from a Formal [3+3] Cycloaddition Reaction of Metal Vinylidene with Alkynols

Zhao

Gong

et al. 2011

Angewandte Chemie

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The investigation on the synthesis and reactivity of metal vinylidene complexes has always been an active area, [1] especially given their applications as well-known catalysts for metathesis and carbon-carbon and carbon-heteroatom coupling reactions. [1b,e, 2] Compared with other reactions of metal vinylidenes, the cyclization reactions are underdeveloped. Previous studies showed that the vinylidene M = C a bond participated in cycloadditions (see a) as key steps in carboncarbon coupling reactions, [3] and some cycloaddition products have also been isolated. [4] Interestingly, similar reactions of the metal vinylidene C a = C b bond (see b) have been realized as well. [5] However, cyclizations of the skeleton of metal vinylidene (M = C a = C b ) as a unit (see c) remain scarce. In fact, the reported cyclization is a formal [3+2] cycloaddition reaction. [5c] To the best of our knowledge, the [3+3] cyclization reactions of metal vinylidene to construct six-membered rings have not been reported.Moreover, since the first isolation of metallabenzene was achieved by Roper and co-workers, [7a] considerable research interest has been attracted in this field. [6,7] Nevertheless, the metallabenzene analogue isometallabenzene, which can be seen as a metal-containing 1,2,4-cyclohexatriene, has not been thoroughly explored. Until now, only the 16e À isometallabenzene[Os{ = C = C(Ph) À CH(Ph) À CH = C(CH 2 Ph)}Cl-(PiPr 3 ) 2 ], prepared by double coupling reactions, was reported by Esteruelas and co-workers in 2004. [8] Herein, we report an unprecedented formal [3+3] cycloaddition reaction between the hydride vinylidene complex [OsHCl 2 -{=C=CH(PPh 3 )}(PPh 3 ) 2 ] (2) and alkynols under mild conditions to give stable 18e À iso-osmabenzenes. The origin of the unexpected stability of these iso-osmabenzene complexes and their isomerization into h 5 -cyclopentadienyl complexes through metalated cyclopentadiene intermediates is also described.Stirring of the osmium hydride alkenylcarbyne complex [OsHCl 2 ( C À C(PPh 3 ) = CHPh)(PPh 3 ) 2 ]BF 4 (1) [9] in a mixture of H 2 O/CH 3 OH (3:2 v/v) at reflux produced the osmium hydride vinylidene complex 2, which was isolated as a lightyellow solid in 60 % yield (Scheme 1). The other product, PhCHO, was detected by 1 H NMR (d = 9.3 ppm; PhCHO) and GC analysis of the reaction mixture (see Figure S1 in the Supporting Information). Complex 2 was characterized by NMR spectroscopy and elemental analysis, and the structure was additionally confirmed by single-crystal X-ray diffraction ( Figure S2).Complex 2 is thermally stable in the solid state but highly reactive in solution. Treatment of 2 with HC CCH(OH)Ph in dichloromethane or chloroform at room temperature led to a fast color change from light yellow to brown red. The unexpected iso-osmabenzene 3 was generated from a formal [3+3] cycloaddition and isolated in high yield (93 %). Similarly, when 2 reacted with HC CCH(OH)CH = CH 2 or HC CCH(OH)CH 2 CH 3 under the same reaction conditions, the other two iso-osmabenzenes, 4 (88 % yield) and...

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Synthesis and Characterization of [OsCl₂(=C=CHR)(PPh₃)₂] and Related Complexes

Cited by 28 publications

References 73 publications

A Metallanaphthalyne Complex from Zinc Reduction of a Vinylcarbyne Complex

A Metallanaphthalyne Complex from Zinc Reduction of a Vinylcarbyne Complex

Osmium(II) and Osmium(IV) Complexes with Phosphane–Ethers, –Esters, and –Amines as Mono‐ and Bidentate Ligands

Stable Iso‐osmabenzenes from a Formal [3+3] Cycloaddition Reaction of Metal Vinylidene with Alkynols

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