Bustos Itxaso, Seco Jose M, Rodriguez-Dieguez Antonio, Garralda María A, Mendicute-Fierro Claudio
Department of Applied Chemistry, Faculty of Chemistry, University of The Basque Country UPV/EHU, Paseo Manuel Lardizabal 3, 20018Donostia-San Sebastián, Spain.
Department of Inorganic Chemistry, Faculty of Science, University of Granada, 18071Granada, Spain.
Organometallics. 2022 Dec 1;41(23):3654-3663. doi: 10.1021/acs.organomet.2c00451. eCollection 2022 Dec 12.
Aliphatic diamines [(HN(CH)NHR) () = 2: R = H (), R = CH (), R = CH (), = 3, R = H () or -2-(aminomethyl)piperidine ()] react with [IrH(Cl){(PPh(-CHCO))H}] in THF to afford ketoimine complexes [IrH(Cl){(PPh(-CHCO))(PPh(-CHCN(CH)NHR))H}] (-) or [IrH(Cl){(PPh(-CHCO))(PPh(-CHCNCH(CHNH)))H}] (), containing a bridging N-H···O hydrogen bond and a dangling amine. Complex consists of an almost equimolar mixture of two diastereomers. In protic solvents, the dangling amine in complexes displaces chloride to afford cationic acyl-iminium compounds, [IrH(PPh(-CHCO))(PPh(-CHCNH(CH)NHR))]X (-, X = Cl) or [IrH(PPh(-CHCO))(PPh(-CHCNHCH(CHNH)))]Cl () and (-, X = ClO), with new hemilabile terdentate PCN ligands adopting a facial disposition. Complexes contain the corresponding phosphorus atom trans to hydride and the amine fragment trans to acyl, while complexes contain the amine to hydride. and consist of 80:20 and 95:5 mixtures of diastereomers, respectively, while contains a 65:35 mixture. In the presence of KOH, intermediate cationic acyl-iminium complexes transform into neutral acyl-imine [IrH(PPh(-CHCO))(PPh(-CHCN(CH)NHR))] derivatives () with retention of the stereochemistry. Single-crystal X-ray diffraction analysis was performed on , []Cl, []Cl, []ClO, and . Complexes , , and catalyze the methanolysis of ammonia-borane under air to release hydrogen. The highest activity is observed for ketoimine complexes .
脂肪族二胺[（HN(CH)NHR）（ = 2：R = H（ ），R = CH（ ），R = CH（ ）， = 3，R = H（ ）或 -2-(氨甲基)哌啶（ ）]与[IrH(Cl){(PPh(-CHCO))H}]在四氢呋喃中反应，得到酮亚胺配合物[IrH(Cl){(PPh(-CHCO))(PPh(-CHCN(CH)NHR))H}]（ ）或[IrH(Cl){(PPh(-CHCO))(PPh(-CHCNCH(CHNH)))H}]（ ），其含有一个桥连的N-H···O氢键和一个游离胺。配合物 由两种非对映异构体的几乎等摩尔混合物组成。在质子溶剂中，配合物 中的游离胺取代氯离子，得到阳离子酰基亚铵化合物，[IrH(PPh(-CHCO))(PPh(-CHCNH(CH)NHR))]X（ ，X = Cl）或[IrH(PPh(-CHCO))(PPh(-CHCNHCH(CHNH)))]Cl（ ）和（ ，X = ClO），具有新的半不稳定三齿PCN配体，呈面式排列。配合物 中磷原子与氢化物处于反位，胺片段与酰基处于反位，而配合物 中胺与氢化物处于 位。 和 分别由80:20和95:5的非对映异构体混合物组成，而 含有65:35的混合物。在KOH存在下，中间阳离子酰基亚铵配合物 转化为中性酰亚胺[IrH(PPh(-CHCO))(PPh(-CHCN(CH)NHR))]衍生物（ ），立体化学保持不变。对 、[]Cl、[]Cl、[]ClO和 进行了单晶X射线衍射分析。配合物 、 和 在空气中催化氨硼烷的甲醇解以释放氢气。酮亚胺配合物 的活性最高。
