Organic chemistry of the iron—ruthenium centre

Gracey, Benjamin P.; Knox, Selby A. R.; Macpherson, Kirsty A.; Orpen, A. Guy; Stobart, Stephen R.

doi:10.1016/0022-328x(84)80490-8

Cited by 16 publications

(23 citation statements)

References 4 publications

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“…The kinetically formed 24 reacts with NMe3 at -78 °C to produce 26. However, when the equilibrium mixture of 24, 25-E, and 25-Z is treated with NMe3 at room temperature, deprotonation of 25-E and 25-Z occurs to produce vinyl car bene complexes 27 and 28 in addition to 26 obtained from 24.34 Therefore, in working up the products from the reaction of 1 with trans-2-butene, either aqueous bicarbonate or NMe3 at -78 °C was employed to cleanly convert the hydrocarbation product to the neutral ju-2-methyl-1 -butenylidene complex 26 for analysis.…”

Section: R=prmentioning

confidence: 99%

See 1 more Smart Citation

Hydrocarbation-formation of diiron .mu.-alkylidyne complexes from the addition of the carbon-hydrogen bond of a .mu.-methylidyne complex across alkenes

Casey¹,

Meszaros²,

Fagan³

et al. 1986

J. Am. Chem. Soc.

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The reaction of [(C5H5)(CO)Fe]2^-CO)^-CH)+PF6•, 1, with ethylene produced [(C5H5)(CO)Fe]2Oi-CO)Ot-CCH2CH3)+PF6", 4, in 68% yield. 4 reacted with trimethylamine to give [(C5H5)(CO)Fe]2(^-CO)(M-C=CHCH3), 5, in 84% yield. 1 reacted regioselectively with propene, 1-butene, 1-pentene, ieri-butylethylene, styrene, butadiene, allylbenzene, and isobutylene to give similar µ-alkylidyne products in 76-85% yields. The syn addition of hydrocarbation was established by the reaction of 1 with (£)-and (Z)-1,2-dideuterio-3,3-dimethyl-1 -butene, 23-E and 23-Z. The rate of the reaction of 1 with fra«s-2-butene at -50 °C followed second-order kinetics with k2 = 9.2 ± 0.7 X 10'1 23 M'1 s'1. Competition techniques were used to measure the relative reactivity of 1 toward alkenes at -50 °C, and electron-donating alkyl substituents substantially increased the reactivity of the alkene. The deuterium kinetic isotope effect for the reaction of 1 with propene and isobutylene at -50 °C was found to be 0.74 ± 0.03 and 0.80 ± 0.03. The regiochemistry, relative rates, and kinetic isotope effects are consistent with a transition state for the rate-determining step of hydrocarbation which involves only initiation of a bond from (21) Casey, C.

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Section: R=prmentioning

confidence: 99%

“…Rate of Reaction of teoní-2-Butene with 1 at -50 °C 103[1], M 103[C4H8], M time, s 103[26], M 103Jt2, M-> s"1 .0 mixture of 24, and µ-2-methyl-1 -butenyl complexes 25-Z and 25-E. At room temperature, aqueous bicarbonatede- …”

mentioning

confidence: 99%

Hydrocarbation-formation of diiron .mu.-alkylidyne complexes from the addition of the carbon-hydrogen bond of a .mu.-methylidyne complex across alkenes

Casey¹,

Meszaros²,

Fagan³

et al. 1986

J. Am. Chem. Soc.

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“…The complex nature of many of these reactions and the myriad number of products often isolated is manifested by the large number of publications that regularly document new reactions in this class. Reactions of bimetallic and heterobimetallic complexes with alkynes continue to receive attention by many groups. − Our contributions to this field described the reactions of Co x M 4 - x (M = Mo, W; x = 1−3) clusters with alkynes; other research by our group has detailed the reactions of coordinatively saturated Ni−M (M = Mo, W) species with alkynes. − …”

Section: Introductionmentioning

confidence: 99%

Reactions of Terminal Alkynes with Group 6−Group 10 Heterobimetallics

1996

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Reactions of PhC2H with NiCp*M(CO)3Cp‘‘ [Ni−M: M = Mo, W; Cp* = η5-C5Me5; Cp‘‘ = Cp (η5-C5H5) or Cp‘ (η5-C5H4Me)] afford metallacyclic species 4, of formula NiCp*{μ-η3(Ni),η1(1-M)C(H)C(Ph)C(O)}M(CO)2Cp (Ni−M, M = Mo, W), as the principal products. These compounds are isomeric to four-membered nickelacycles obtained in similar reactions with disubstituted alkynes and contain five-membered NiC(O)C(H)C(Ph)M ring systems. Phenylacetylene also affords minor quantities of alkyne bridged complexes with “dimetallatetrahedrane-type” nuclear cores. Alkylation of 4 with (Me3O)+BF4 - results in the methylation of the metallacyclic (acyl-like) carbonyl ligand and a structural rearrangement ensues: cationic four-membered molybdena- or tungstenacycles 6 of formula [NiCp*{μ-η3(Ni),η2(1,3-M)C(H)C(Ph)C(OMe)}M(CO)2Cp]+BF4 - (Ni−M, M = Mo, W) result. An iodide-for-carbonyl substitution reaction on 6 affords the neutral complexes 8 [NiCp*{μ-η3(Ni),η2(1,3-M)C(H)C(Ph)C(OMe)}MI(CO)Cp] (Ni−M), which maintain the structural core present in 6. The structure of 8b‘, [NiCp*{μ-η3(Ni),η2(1,3-W)C(H)C(Ph)C(OMe)}WI(CO)Cp‘] (Ni−W) was established by X-ray diffraction.

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“…Both ring systems have been observed previously in homo-and in heterobimetallic systems. In our previously reported reactions of complex 1a with PhC 2 H, both complexes were obtained, but in most cases in the literature, there is a preference for one or the other isomer [8,9,[17][18][19][20][21][22][23][24][25][26]. With the bulky DPMP ligand, a five-membered dimetallacyclopentenone ring system might have been expected, but this isomer of complexes 3 is not observed.…”

Section: Resultsmentioning

confidence: 64%

“…Alkyne-carbonyl coupling reactions on bimetallic complexes to form CR-CR 0 -C(O) moieties have been reported by us and by others. This C 3 chain may either be r-bonded to a single metal of the bimetallic center, to form a four-membered [8,9,[17][18][19][20], [21][22][23][24][25][26]. (The CR@CR 0 AC(O) group is also known to bond to a di-metal center in other, non-cyclic bonding modes [27,28]).…”

Section: Resultsmentioning

confidence: 98%