151240-99-2Relevant articles and documents
Synthesis and reactivity of (η6-arene)(phosphino enolato)ruthenium(II) complexes, their coupling reaction with phenylacetylene, and thermal rearrangement to a phosphametallacyclopropane. X-ray crystal structures of {Ru[η3-CH=C(Ph)CH(PPh2)C(Bu t)=O](p-cymene)}(PF6), of {Ru[η3 ...
Demerseman, Bernard,Guilbert, Bénédicte,Renouard, Corinne,Gonzalez, Marta,Dixneuf, Pierre H.,Masi, Dante,Mealli, Carlo
, p. 3906 - 3917 (2008/10/08)
Full title: Synthesis and reactivity of (η6-arene)(phosphino enolato)ruthenium(II) complexes, their coupling reaction with phenylacetylene, and thermal rearrangement to a phosphametallacyclopropane. X-ray crystal structures of {Ru[η3-CH=C(Ph)CH(PPh2)C(Bu t)=O](p-cymene)}(PF6), of {Ru[η3-CH=C(Ph)C(Me)(PPh 2)C(Et)=O](mesitylene)}(BF4), and of {Ru[η3-CH(PPh2)CPh=C(H)C(Bu t)=O](mesitylene)}(BF4). The reaction of lithium enolates with chlorodiphenylphosphine provides a convenient large scale synthesis of β-keto phosphines. The coordination of β-keto phosphines 1 at an (η6-arene)Cl2Ru fragment affords neutral complexes (η6-arene)Cl2Ru[η1-P-Ph 2PCHR2C(=O)R1], 2, cationic complexes {(η6-arene)ClRu[η2-P,O-Ph2PCR 3R2C(R1)=O]}+, 3, and neutral enolato derivatives (η6-arene)ClRu[η2-P,O-OC(R1)=C(R 2)PPh2], 4. Compounds 4 react under mild conditions with ligands L (L = Me2S or RC≡N) to give cationic derivatives {(η6-arene)(L)ClRu[OC(R1)=C-(R2)PPh 2]}+, 5. When L is PhC≡CH, carbon - carbon bond formation leads via regioselective coupling of the C≡C bond to both ruthenium and =C(PPh2) carbon to complexes {(η6-arene)Ru[η3-CH=C(Ph)C(R2)(PPh 2)C(R1)=O]}+, 6. The crystal structures of the compounds 6a (arene = p-cymene, R2 = H, R1 = But), monoclinic, space group P21/n (No. 14) with Z = 4, a = 14.870(4) A?, b = 20.087(6) A?, c = 12.454(5) A?, α = 90.0°, β = 92.67(3)°, γ = 90.0°, d(calcd) = 1.37 g/cm3, and 6c (arene = mesitylene, R2 = Me, R1 = Et), triclinic, space group P1 (No. 2) with Z = 2, a = 10.962(1) A?, b = 15.473(2) A?, c = 10.910(1) A?, α = 100.10(1)°, β = 113.64(1)°, γ = 102.41(1)°, d(calcd) = 1.55 g/cm3, have been determined. 6b (arene = mesitylene, R2 = H, R1 = But) is cleanly thermally converted to the metallaphosphacyclopropane derivative {Ru[η3-CH(PPh2)CPh=C(H)C(BU t)=O](mesitylene)}+, 7, as shown by the X-ray structure determination: triclinic, space group P1 (No. 2) with Z = 2, a = 14.034(2) A?, b = 11.944(1) A?, c = 10.957(1) A?, α = 106.56°, β = 98.34(1)°, β = 109.24(1)°, d(calcd) = 1.44 g/cm3.
