87937-39-1Relevant academic research and scientific papers
Reactivity of diphosphenes, phospharsenes, and diarsenes toward transition-metal carbonyls
Cowley,Kilduff,Lasch,Norman,Pakulski,Ando,Wright
, p. 1044 - 1050 (2008/10/08)
The reactivity of stable diphosphenes, phospharsenes, and diarsenes toward transition-metal carbonyls has been explored. The diphosphene (2,4,6-t-Bu3C6H2)P2, 2, forms adducts with one Fe(CO)4 and one Ni(CO)3 group from reactions with Fe2(CO)9 and Ni(CO)4, respectively. The iron complex (2,4,6-t-Bu3C6H2)2P 2Fe(CO)4, 3, has been structurally characterized by X-ray diffraction. Compound 3 crystallizes in the monoclinic space group P21/c, with a = 21.251 (6) ?, b = 9.793 (2) ?, c = 20.99 (2) ?, and β = 108.73 (6)°. The structure reveals that the diphosphene 2 is η1 bonded to the Fe(CO)4 group through a phosphorus lone pair. The phospharsene 2,4,6-t-Bu3C6H2As=PCH(SiMe3) 2, 8, reacts with Fe2(CO)9 to give complexes with an Fe(CO)4 group attached to As, 9, or P, 10. Treatment of the diarsene 2,4,6-t-Bu3C6H2As= AsCH(SiMe3)2, 11, with Cr(CO)5(THF) affords the complex 2,4,6-t-Bu3C6H2As=AsCH(SiMe3) 2Cr(CO)5, 12, with the Cr(CO)5 unit η1 bonded to the (Me3Si)2CH-substituted arsenic. This was determined by an X-ray diffraction study. Compound 12 crystallizes in the monoclinic space group P21/n with n = 10.710 (3) ?, b = 29.770 (3) ?, c = 11.984 (1) ?, and β = 98.02 (1)°. The structures of and bonding in these complexes are discussed.
