| 257283-36-6

• CAS: 257283-36-6
• 化学式: C₄₄H₃₈NO₅P₂Rh
• 分子量: 825.642
• InChiKey: VUTBXSRZJWEHKT-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  丁炔二酸二甲酯 、 [Rh(CO)(P(phenyl)3)(2-(phenyl)2PC6H4NCH3-κN,κP)] 以 甲苯 为溶剂， 以72%的产率得到
  参考文献：
  名称：

  Rhodium and iridium complexes with 2-(diphenylphosphanyl)anilido ligands: reactions with phenylacetylene and dimethyl acetylenedicarboxylate †

  摘要：

  Treatment of [Ir(CO)(PPh3)(‘PNMe’)] (‘PNMe’ = 2-Ph2PC6H4NMe–) with phenylacetylene resulted in oxidative addition and opening of the chelate ring to afford mono- and bis-(alkynyl) derivatives, [IrH(CCPh)(CO)(PPh3)(‘PNMe’)] 1 and [IrH(CCPh)2(CO)(PPh3)(η1-‘PN(Me)H’)] 2, respectively. Complex 2 exists as two isomers with trans-located phosphane ligands and cis- or trans-coordinated alkynyl groups. The minimum values of the spin–lattice relaxation times, T1(min), observed for the hydride ligands of the two isomers ruled out the possibility of short IrH· · ·HN contacts in 2. Combination of [Ir(CO)(PPh3)(‘PNMe’)] with dimethyl acetylenedicarboxylate (dmad) gave the irida(III)cyclopropene-like complex [Ir{C2(CO2Me)2}(CO)(PPh3)(‘PNMe’)] 3 as the expected 1∶1 adduct. In contrast, [Rh(CO)(PPh3)(‘PNMe’)] and dmad interacted by insertion of the activated alkyne into the Rh–N bond, forming the seven-membered metallaheterocycle [Rh{C(CO2Me)C(CO2Me)N(Me)C6H4PPh2-2}(CO)(PPh3)] 4. [Ir(CO)(PPh3)(‘PNH’)] (‘PNH’ = 2-Ph2PC6H4NH–) and dmad reacted to initially produce a mixture of metallacyclic [Ir{C2(CO2Me)2}(CO)(PPh3)(‘PNH’)] 5 and unchanged starting materials. Subsequent treatment with methanol resulted in the formation of the iridium(III) complex [Ir{C(O)OMe}{C(CO2Me)CH[C(O)OMe]}(PPh3)(‘PNH’)] 6, which X-ray crystallography showed to contain a chelating vinyl ligand featuring substantial carbenoid character.

  DOI：

  10.1039/a906430c