Nucleophilic Attack on Unsaturated Hydrocarbons Coordinated to Transition Metals

Author:

Davies S. G.,Green M. L. H.,Mingos D. M. P.

Publisher

Springer US

Reference168 articles.

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3. M.L.H. Green and P.L.I. Nagy, J. Organomet. Chem. 1: 581 (1963).

4. M.F. Semmelhack, Ann. N.Y. Acad. Sci. 36 (1977).

5. G. Jaouen in “Transition Metal Organometallics in Organic Synthesis”, Vol. 2, H. Alper ed., Academic Press, London and New York, 1978, p. 105.

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4. Hydrocarbon‐bridged Metal Complexes, XXI. – Addition of Tetracarbonylosmate and ‐ruthenate to Coordinated Unsaturated Hydrocarbons: Trinuclear Complexes with two σ,α‐Allyl, Methylallyl, Cyclohexadiene, Cycloheptadiene, Cyclohexadienyl, Cycloheptatrien, and “Thiophene” Bridges The addition of organometallic nucleophiles [M(CO) 4 ] 2‐ (M = Os, Ru) to [(Cp)(ON)(OC)Mo(allyl)] + , [Cp(OC) 2 Mo(butadiene)] + , [(OC) 3 Fe(cycloheptadienyl)] + , [(OC) 3 Fe(cycloheptadienyl)] + , [(OC) 3 Mn(benzene)] + , [(OC) 3 Mn(thiophene)] + , [(OC) 3 ‐Mo(cycloheptatrienyl)] + leads to the heterotrimetallic η 1 :η 2 ‐, η 1 :η 3 ‐, η 1 :η 4 ‐, η 1 :η 5 ‐, η 1 :η 6 ‐hydrocarbon‐bridged complexes 1 ‐ 7. The structures of cis ‐(OC) 4 Os[(μ‐η 1 :η 4 ‐C 7 H 9 )Fe(CO) 3 ] 2 (4), cis ‐(OC) 4 Os[(μ‐η 1 : 5 ‐C 6 H 6 ‐Mn(CO) 3 ] 2 (6), and cis ‐(OC) 4 Os‐[μ‐η 1 :η 6 ‐C 7 H 7 ‐Mo(CO) 3 ] 2 (7b) have been determined by X‐ray analysis. The fluxional behaviour of 6 in solution has been studied in a temperature range from – 70 to +60°C. The comparison of observed and calculated 1 H‐NMR data indicates a 1,2‐shift mechanism (ΔG + = 49 kJ/mol).;Chemische Berichte;1991-10

5. Kohlenwasserstoffverbrückte Komplexe XX Nucleophile Addition von Carbonylmetallaten an kationische Hexadienyl‐, Cycloheptadienyl‐, Cycloheptadienyl‐ und Cyclooctadienyl‐Komplexe von Eisen und Ruthenium: Heterodimetall‐Komplexe mit η 1 :η 4 ‐C 6 ‐, ‐C 7 ‐ und ‐C 8 ‐Kohlenwasserstoffbrücken;Chemische Berichte;1991-10

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