Crystal and molecular structure of phenyltrimethylenemethaneiron tricarbonyl

Gold, Karen

doi:10.1021/ic50073a001

Cited by 34 publications

(9 citation statements)

References 5 publications

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“…Thus, Mo-C( 1,5) > Mo-C(2,4) > Mo-C(3), demonstrating that the ligand is slightly tilted away from C (22) and C(33), and H * -H contacts of 2.03,2.05, and 2.07 A exist between H(31) and H(63) and H(62), and H (21) and H( 103), respectively. Although, consistent with this, 22 * Z is the centroid of the cyclopentadienyl ring and has fractional co-ordinates -0.015 76 (16), 0.198 18(18), 0.161 71 (9). but shows a small distortion towards an envelope fold across C(2) * C(4) of 1.4", away from the metal atom.…”

Section: Resultssupporting

confidence: 54%

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Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η⁴-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η⁴-C(CH₂)₃}(CO)₂(η-C₅Me₅)][BF₄]

Allen¹,

Barnes²,

Green³

et al. 1984

J. Chem. Soc., Dalton Trans.

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Reaction of [Mo~(CO),(~-C,M~,)~] with methylenecyclopropane and AgBF, in CH2CI2 affords the cationic trimethylenemethane complex [Mo{q4-C(CH2) 3)( CO) 2(q-C5Me5)] [B F, ] . Methylenecyclopropane and 2,2-dimethylmethylenecyclopropane react with [Mo( NCMe),(CO),(q-C,H,)][ BF4][BF,] confirmed that ring opening of methylenecyclopropane had occurred. The complex crystallises in the centrosymmetric orthorhombic space group Pbca with a = 12.822(2), b = 12.31 1 (3), c = 22.660(4) A, and Z = 8 ion pairs. The structure has been solved by conventional methods and refined by fullmatrix least squares to R = 0.0674 for 2 747 observed reflections at 268 f 1 K. In the cation the trimethylenemethane ligand adopts an orientation that is syn with respect to the OC-Mo-CO angle. It is pyramidal with the CH2 groups bent towards the molybdenum atom by an average of 12.4'. There is intramolecular congestion involving the C,Me5 and C(CH2)3 ligands that may contribute towards the observed asymmetric bonding of the former to the metal atom. Extended Huckel molecular-orbital calculations suggest that the observed syn stereochemistry is electronically preferred, and that the barrier to rotation of the T ~, -C ( C H ~) ~ ligand relative to a Mo(CO),(q-C,H,)fragment is high. The stereochemistry of the ring-opening reaction is disrotatory-out as exemplified by the conversion of cisand trans-2,3-dimethylmet hylenecyclopropane into syn,syn-dimet hyl and syn,anti-dimet hyl-trimethylenemethane complexes. The reaction of these cationic q4-trimethylenemethane complexes with the nucleophiles BH4 -, OH-, CuMe,-, and SPh-affords q3-allylic complexes derived from attack on the peripheral carbons.to giveMethylenec>clopropanes react with compounds of Fe', Rh', Ir', Pt ", and Pt' to form simple q2-bonded alkene complexes in which the three-membered ring remains i n t a ~t . ~. ~ However, these small-ring compounds are also known to undergo transition-metal-mediated reactions where carbon-carbon cleavage occurs. This is illustrated by the reaction of [Fez-(CO),] with methylene-2-phenylcyciopropane forming tricarbonyl( q4-trimet hylenephenylmet hane)iron, a detailed study with deuterium-labelled methylene-2-phenylcyclopropane showing that a distotatory-out ring-opening reaction occurs. Furthermore, a recent study of the chloropalladation reactions of methylenecyclopropanes carrying alkyl substituents on the three-membered ring showed that cleavage of the 2.3-0 bond occurred in a disrotatory manner. Ring cleavage also occurs in the palladium(0)-catalysed cycloaddition reactions of methylenecyclopropanes, although the question as to whether these reactions involve q4-trimethylenemethane complexes remains to be answered. We had previously observed that [ M o ( C O ) ~( ~-C , M ~, ) ] + reacts with methylenecyclopropane to form the first cationic q4-bonded trimethylenemethane complex, and this paper describes a detailed study of this reaction.$ Prepared by protonation (HBF,-Et20) of [MoM~(CO)~(T&H~)] dissolved in CHzCIz followed by reaction with MeCN.'j

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Section: Resultssupporting

confidence: 54%

“…For the complex [Fe{q4-C(CH2)3}(C0)3] Is 8 = 13.6" and 0 = 14.4", and in the case of [Fe(q4-C(CH,)zCHPh>(CO)3] 0 values of 13.9, 13.0, and 1 1.7" are recorded. 16 Tricarbonyl(q4-7methylenecyclohepta-1,3,5-triene)iron also contains an irortrimethylenemethane linkage, with 8 = 11.0, 10.1, and 10.1' and…”

Section: Resultsmentioning

confidence: 99%

Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η⁴-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η⁴-C(CH₂)₃}(CO)₂(η-C₅Me₅)][BF₄]

Allen¹,

Barnes²,

Green³

et al. 1984

J. Chem. Soc., Dalton Trans.

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“…The 3 [38] and h 4 -[C(CH 2 ) 2 (CHPh)]Fe(CO) 3 [39] are in a staggered conformation in relation to the CO groups. The Fe(CO) 3 and C(1)MnC(2)C(3) fragments of 2 and 4 (see Fig.…”

Section: X-ray Diffraction Study Of H 4 -{C[mn(co)(pph 3 )Cp](co)chphmentioning

confidence: 99%

Chemistry of vinylidene complexes. XX. Intramolecular carbonylation of vinylidene on the MnFe center: Spectroscopic and structural study. X-ray structure of the new trimethylenemethane type MnFe complex

Antonova

Чудин

Vasiliev

et al. 2011

Journal of Organometallic Chemistry

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“…These vinylideneketene ligands which do not exist as free molecules are bound to one of the metal centers in h 3 -allylic fashion, featuring one s-bond to the second metal center. This h 3 -allylic ligand together with a metal-containing fragment e Cp(CO) 2 Mn or (Et 3 P)(CO) 3 Fe e represents a heterometallic analog of the trimethylenemethane (TMM) ligand C 1 (CH 2 ) 3 [7]. The ligand PhC 2 H] C 1 ]C 3 ]O of the diplatinum complex (C 6 F 5 ) 2 (PPh 3 )Pt[(h 3 -PhC 2 HC 1 C 3 O)Pt(PPh 3 ) 2 ] is of p-allylic type [6].…”

Section: Introductionmentioning

confidence: 99%

Vinylidene carbonylation at a manganese–iron complex: A density functional study of mechanism

Ivanova-Shor

Наслузов

Shor

et al. 2011

Journal of Organometallic Chemistry

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Crystal and molecular structure of phenyltrimethylenemethaneiron tricarbonyl

Cited by 34 publications

References 5 publications

Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η⁴-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η⁴-C(CH₂)₃}(CO)₂(η-C₅Me₅)][BF₄]

Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η⁴-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η⁴-C(CH₂)₃}(CO)₂(η-C₅Me₅)][BF₄]

Chemistry of vinylidene complexes. XX. Intramolecular carbonylation of vinylidene on the MnFe center: Spectroscopic and structural study. X-ray structure of the new trimethylenemethane type MnFe complex

Vinylidene carbonylation at a manganese–iron complex: A density functional study of mechanism

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Crystal and molecular structure of phenyltrimethylenemethaneiron tricarbonyl

Cited by 34 publications

References 5 publications

Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η4-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η4-C(CH2)3}(CO)2(η-C5Me5)][BF4]

Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η4-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η4-C(CH2)3}(CO)2(η-C5Me5)][BF4]

Chemistry of vinylidene complexes. XX. Intramolecular carbonylation of vinylidene on the MnFe center: Spectroscopic and structural study. X-ray structure of the new trimethylenemethane type MnFe complex

Vinylidene carbonylation at a manganese–iron complex: A density functional study of mechanism

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Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η⁴-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η⁴-C(CH₂)₃}(CO)₂(η-C₅Me₅)][BF₄]

Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η⁴-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η⁴-C(CH₂)₃}(CO)₂(η-C₅Me₅)][BF₄]