228551-62-0Relevant academic research and scientific papers
Insertion of strongly electron withdrawing cyanoolefins into the C-H bond in pentamethylcyclopentadienyl-rhodium(III) and -iridium(III) complexes containing P-O or P-O-O′ coordinations
Yamamoto,Han,Nishimura,Sugawara,Nezu,Tanase
, p. 266 - 272 (2001)
Complexes, Cp*MCl(MDMPP-P,O) (1a: M = Rh, 1b: M = Ir; Cp* = η5-C5Me5; MDMPP-P,O = PPh2(C6H3-2-O-6-MeO)) readily react with tcne or tcnq to form the 1:1 adducts [Cp*MCl(MDMPP-P,O)(ol)] (ol = tcne (c), tcnq (d)) (3ac: M = Rh, ol = tcne; 3bc: M = Ir, ol = tcne; 4ad: M = Rh, ol = tcnq; 4bd: M = Ir, ol = tcnq), derived from insertion of cyanoolefins into the C-H bond adjacent to the metal-O bond. Complex Cp*Ir(TDMPP-P,O,O′) 2b (TDMPP-P,O,O′ = P{C6H3-2,6-(MeO)2}(C6H3-2-O-6-MeO)2) bearing a (P,O,O′) coordination was treated with 1 equiv of tcne, tcnq, or Me2-tcnq (e) to give the products in which one molecule of cyanoolefin was inserted, [Cp*Ir(TDMPP-P,O,O′)(ol)] (5bc: ol = tcne; 6bd: ol = tcnq; 6be: ol = Me2-tcnq). Reactions with 2 equiv of cyanoolefin gave the products [Cp*Ir(TDMPP-P,O,O′)(ol)2] (7bc: ol = tcne; 8bd: ol = tcnq), in which insertion occurred at two C-H positions adjacent to the Ir-O bonds. Structural data for 3ac, 3bc, 4ad, 5bc, and 7bc are described.
