147282-50-6Relevant academic research and scientific papers
An unorthodox reaction of indene with ReH7(PPh3)2: The competitive formation of an η5-indanyl ligand versus an η5-indenyl ligand
Rosini, Glen P.,Jones, William D.
, p. 965 - 974 (2007/10/02)
The reaction of indene with ReH7(PPh3)2 yields a mixture of two organometallic complexes, identified as (η5-C9H7)ReH2(PPh 3)2 (1) and (η5-C9H11)ReH2(PPh 3)2 (2). In 1, the minor (expected) product, the metal is η5-bound to the five-membered ring, while in 2, the major product, the metal is η5-bound to the six-membered ring. When the reaction is run in the presence of 3,3-dimethyl-l-butene, only 1 is formed, while 2 can be obtained pure if the reaction is run under an atmosphere of hydrogen. The mechanism for the formation of 1 and 2 is discussed, as are the photochemical and thermal reactivities of 2, leading to the formation of (η6-C9H10)ReH3(PPh3) (5) and (η6-C9H10)ReH(PPh3)2 (6), respectively. When bfcyclo[4.3.0]nona-3,6(l)-diene is used in place of indene, the product is the unexpected 2,4-diene complex (η4-C9H12)ReH3(PPh 3)2 (7), which rearranges upon heating to a 1:1.5 mixture of 2 and a complex analogous to 1 with an η5-bound 4,5,6,7-tetrahydroindene ligand (η5-C9H11)ReH2(PPh 3)2 (8). Oxidation/protonation of complex 2 results in the formation of complex 9 or 10, [(η6-C9H10)ReH2(PPh 3)2][X] (X = ReO4,9; BF4,10). Complex 1 crystallizes in the triclinic space group P1? with a = 9.876 (7) A?, b = 14.137 (4) A?, c = 14.375 (12) A?, α = 96.12 (6)°, β = 109.07 (6)°, γ = 107.99 (5)°, V= 1755 (2) A?3, and Z = 2. Complex 2 crystallizes in the triclinic space group P1? with a = 10.140 (4) A?, b = 13.993 (5) A?, c = 14.564 (9) A?, α = 95.51 (4)°, β = 109.73 (4)°, γ = 107.58 (3)°, V = 1809 (4) A?3, and Z = 2. Complex 5 crystallizes in the triclinic space group P1? with a = 8.626 (3) A?, b = 9.201 (2) A?, c = 16.002 (5) A?, α = 97.43 (2)°, β = 98.34 (3)°, γ = 114.12 (3)°, V = 1122 (1) A?3, and Z = 2. Complex 6 crystallizes in the monoclinic space group P21/n with a = 10.428 (3) A?, b = 17.054 (3) A?, c = 20.100 (4) A?, β = 98.78 (2)°, V = 3532 (1) A?3, and Z = 4. Complex 7 crystallizes in the monoclinic space group P21/n with a = 14.418 (2) A?, b = 16.823 (4) A?, c = 15.838 (7) A?, β = 102.72 (2)°, V = 3747 (3) A?3, and Z = 4. Complex 8 crystallizes in the triclinic space group P1? with a = 10.104 (3) A?, b = 14.344 (5) A?, c = 14.475 (5) A?, α = 71.85 (3)°, β = 69.42 (2)°, γ = 71.01 (2)°, V = 1811 (1) A?3, and Z = 2. Complex 9 crystallizes in the monoclinic space group P21/n with a = 11.950 (3) A?, b = 18.836 (8) A?, c = 17.781 (5) A?, β = 98.28 (2)°, V = 3961 (4) A?3, and Z = 4.
