J. M. Butler, A. Jablonsky, G. M. Gray
Jan 30, 2003
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0
Influential Citations
18
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Journal
Organometallics
Abstract
Chlorodiphenylphosphine and 2,2‘-biphenylylenephosphorochloridite react with 2-hydroxy-2‘-(1,4,7-trisoxo-9-nonanol)-1,1‘-biphenyl to yield the new α,ω-bis(phosphorus-donor)polyether ligands Ph2PO(CH2CH2O)3-2-C12H8-2‘-OPPh2 and (2,2‘-O2C12H8)P(CH2CH2O)3-2-C12H8-2‘-P(2,2‘-O2C12H8). These ligands react with Mo(CO)4(nbd) to form the monomeric cis-metallacrown ethers cis-Mo(CO)4{Ph2PO(CH2CH2O)3-2-C12H8-2‘-OPPh2} and cis-Mo(CO)4{(2,2‘-O2C12H8)P(CH2CH2O)3-2-C12H8-2‘-P(2,2‘-O2C12H8)}. The X-ray crystal structure of cis-Mo(CO)4{(2,2‘-O2C12H8)P(CH2CH2O)3-2-C12H8-2‘-P(2,2‘-O2C12H8)} indicates that in the solid state three of the four metallacrown ether ring oxygens point away from the cavity in the cis-metallacrown ether ring. Both metallacrown ethers undergo cis−trans isomerization in the presence of catalytic amounts of HgCl2 but yield quite different products, cis-Mo(CO)4{Ph2PO(CH2CH2O)3-2-C12H8-2‘-OPPh2}·HgCl2 and trans-Mo(CO)4{(2,2‘-O2C12H8)P(CH2CH2O)3-2-C12H8-2‘-P(2,2‘-O2C12H8)}·HgCl2, when reacted with a stoi...