The synthesis and structure of the chelate olefincarbamylate complexes of iron carbonyls

Nesmeyanov, A. N.; Sal'nikova, T.N.; Struchkov, Yu. T.; Andrianov, V. G.; Pogrebnyak, A. A.; Rybin, L. V.; Rybinskaya, M. I.

doi:10.1016/s0022-328x(00)87995-4

Cited by 21 publications

(11 citation statements)

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“…Earlier we had found NMR evidence for a metastable tungsten-carbene-alkene complex formed from (butenyloxy)carbene complex 1 and showed that this complex was an intermediate in the formation of cyclopropane 2. In this paper, we have exploited the stabilizing effect of amino groups on metal-carbene complexes to prepare the very stable tungsten-carbene-alkene complex 5 in which the carbene and alkene ligands have a nearly perpen- dicular conformation. However, decomposition of 5 did not produce a cyclopropane, probably due to the instability of the required bicyclo[2.1.0] ring system.…”

Section: Discussionmentioning

confidence: 99%

“…For (Z)-4: NMR (270 MHz, C6D6) 1.90 (q, J = 6.5 Hz, 2 H), 2.07 (s, 3 H), 3.52 (q, J = 6.1 Hz, 2 H, NCH2), 4.9 (m, 2 H), 5.45 (m, 1 H), 6.79 (d, J = 6.8 Hz, 2 ), 6.91 (d, J = 7.0 Hz, 2 ), 7.70 (br s, 1 H); 13C NMR (50 MHz, gated decoupled, CD3CN, 0.07 M Cr(acac)3) 21.0 (q, J = 127 Hz, CH3), 33.6 (t, J = 127 Hz, NCH2CH2), 55.4 (t, (26) Bodner, G. M.; Kahl, S. B.; Bork, K.; Storhoff, B. N.; Wuller, J. E.; Todd, L. J. Inorg. Chem.…”

Section: Methodsmentioning

confidence: 99%

“…First, the observation that different [(Z)-3]:[(£)-3] ratios are seen during their conversion to 5 and 6 requires that the equilibration of (Z)-3 and (£)-3 be slow relative to decomposition. Second, (Z)-3 decomposes more rapidly than (£)-3, and its decomposition leads predominantly to carbene-alkene complex 5 (compare data at 19 h). The more rapid disappearance of (Z)-3 causes the [(Z)-3]:[(£)-3] ratio to decrease with time.…”

Section: •Lmentioning

confidence: 99%

“…Similarly, reaction of l-amino-3-butene with (CO)5W=C-(OCH3)C6H4-p-CH3 gave an 87% yield of an isomeric mixture of pentacarbonyl [(3-butenylamino)(p-tolyl)carbene] tungsten(O) ([(Z)-4]:[(£)-4] = 1.9:1], of the pentacarbonyl[(allylamino)carbene]tungsten complex, (Z)-3 and (E)-3, leads to explusion of CO and formation of the chelated metal-carbene-alkene complex cii-tetracarbonyl[(Z)-(p2-allylamino) (p-tolyl)carbene] tungsten(O), 5. When a mixture of (Z)-3 and (£)-3 was heated at 90 °C in toluene for 19 h, metal-carbene-alkene complex 5 was formed and isolated as a yellow crystalline solid in 29% yield following silica gel chromatography.…”

Section: •Lmentioning

confidence: 99%

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Synthesis and x-ray structure of cis-tetracarbonyl[(Z)-(.eta.2-allylamino)(p-tolyl)carbene]tungsten(0), a stable metal-carbene-alkene complex

Casey¹,

Shusterman²,

Vollendorf³

et al. 1982

J. Am. Chem. Soc.

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Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: •Lmentioning

confidence: 99%

Section: •Lmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis and x-ray structure of cis-tetracarbonyl[(Z)-(.eta.2-allylamino)(p-tolyl)carbene]tungsten(0), a stable metal-carbene-alkene complex

Casey¹,

Shusterman²,

Vollendorf³

et al. 1982

J. Am. Chem. Soc.

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“…[28,29] This was followed by several further examples in the intervening years. [30][31][32][33][34][35][36][37][38][39] Functional groups, associated with the carbene, included P, O, S and N atoms as potential donors.…”

Section: Introductionmentioning

confidence: 99%

Donor‐Functionalised N‐Heterocyclic Carbene Complexes of Group 9 and 10 Metals in Catalysis: Trends and Directions

2008

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This review focuses on the latest advances in homogeneous catalysis with donor‐functionalised (donor = C, N, O, S or P) N‐heterocyclic carbene complexes of group 9 and 10 metals. The applications of such complexes to C–C coupling reactions, alkyne and ketone hydrosilylation, olefin polymerisation, transfer hydrogenation, asymmetric hydrogenation and other catalysed reactions are discussed.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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The Chemistry of Metallacyclic Alkenylcarbene Complexes, 4. Unsaturated Metallacyclic Carbene Complexes as Flexible Tools in Organic Synthesis. Novel Rearrangement and Cascade Pathways to Functionalized Alkadienes, Carbo‐, and Heterocycles

Schobert

1996

Chem. Ber.

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Cationic metallacyclic carbene complexes of iron and cobalt bearing a terminal q3-allyl ligand are susceptible to nucleophilic attack at different sites depending on the particular set of substituents, the central metal fragment, and the nucleophile. Attack of enolates, cuprates, acetylides, or heteroatom nucleophiles like phosphanes at the metallacyclic provided. perimeter of the iron complexes 18 provides an easy access to unsaturated organic products like 1,2-or 1,3-dienes, &lactones, and functionalized cyclopentenones through novel rearrangement or cascade pathways. Synthetic applications are described; factors governing reactivity/selectivity are discussed; X-ray analytical structures of novel metallacycles are Rainer Schobert was born in Zell, Bavaria, in 1956. He studied chemistry at the Friedrich-Alexander University, Erlangen, where he received his doctoral degree (1985) jor his work with Hans-JiiPgen Bestmann on novel syntheses of mucrolide antibiotics. In 1993, he finished his Habilitation on stoichiometric reactions and applications of early transition metallocenes. His interest in late transition metal compounds stems from postdoctoral studies with Steven l ? Ley in I990 who inspired all of his coworkers with his enthusiasm for organoiron chemistry. Currently a Privatdozent at Erlangen, Dr. Schobert's research interests include cascade syntheses of unsaturated systems, carbo-, and heterocycles by means of organo-element reagents including cumulated phosphoranes, eurly transition metallocenes, and metallacyclic carbene complexes.

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The synthesis and structure of the chelate olefincarbamylate complexes of iron carbonyls

Cited by 21 publications

References 5 publications

Synthesis and x-ray structure of cis-tetracarbonyl[(Z)-(.eta.2-allylamino)(p-tolyl)carbene]tungsten(0), a stable metal-carbene-alkene complex

Synthesis and x-ray structure of cis-tetracarbonyl[(Z)-(.eta.2-allylamino)(p-tolyl)carbene]tungsten(0), a stable metal-carbene-alkene complex

Donor‐Functionalised N‐Heterocyclic Carbene Complexes of Group 9 and 10 Metals in Catalysis: Trends and Directions

The Chemistry of Metallacyclic Alkenylcarbene Complexes, 4. Unsaturated Metallacyclic Carbene Complexes as Flexible Tools in Organic Synthesis. Novel Rearrangement and Cascade Pathways to Functionalized Alkadienes, Carbo‐, and Heterocycles

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