共 39 条
Mechanistic Study of Acetate-Assisted C-H Activation of 2-Substituted Pyridines with [MCl2CP*]2 (M = Rh, Ir) and [RuCl2(p-cymene)]2
被引:115
作者:
Boutadla, Youcef
[1
]
Al-Duaij, Omar
[1
]
Davies, David L.
[1
]
Griffith, Gerald A.
[1
]
Singh, Kuldip
[1
]
机构:
[1] Univ Leicester, Leicester LE1 7RH, Leics, England
基金:
英国工程与自然科学研究理事会;
关键词:
PROTON-ABSTRACTION MECHANISM;
DIRECT ARYLATION;
ASTERISK-IR;
BOND ACTIVATION;
COMPLEXES;
PALLADIUM;
CYCLOMETALATION;
RUTHENIUM(II);
LIGANDS;
IRIDIUM;
D O I:
10.1021/om800909w
中图分类号:
O61 [无机化学];
学科分类号:
070301 ;
081704 ;
摘要:
Reactions of 2-substituted pyridines HL with [MCl2CP*](2) (M = Ir, Rh) and [RuCl2(p-cymene)](2) have been carried out in the presence and absence of sodium acetate. 2-Phenylpyridine (HLI) is cyclometalated easily to form [MCl(LI)(ring)] 1a-c (M = Rh, Ir, ring = Cp*; M = Ru, ring = p-cymene). However, in the case of 2-acetylpyridine (HL2) sp(3) C-H activation occurs cleanly with rhodium to form N,C chelate complex [RhCl(L2)Cp*] 2b, but the reactions with iridium and ruthenium give unseparable mixtures of products. The N,C cyclometalated products [MCl(L2)(ring)] 2a-c (M = Ir, Rh, ring = Cp*; M = Ru, ring = p-cymene) have been independently prepared from the lithium enolates of 2-acetylpyridine. Notably, in the absence of acetate, [[RhCl2CP*](2) shows no reaction with 2-acetylpyridine, whereas [IrCl2CP*](2) and [RuCl2(p-cymene)](2) react to form equilibrium mixtures of the starting materials and N,O chelate complexes 4a,c, respectively. In the presence of KPF6 the N,O chelate complexes [MCl(HL2)(ring)j[PF6] 4a,c,d (M = Ir, ring = Cp*; M = Ru, ring = p-cymene, mesitylene) can be isolated. These are not intermediates en route to the N,C cyclometalated products. These results suggest that for C-H activation to occur under these mild conditions acetate must coordinate to the metal prior to coordination of the ligand.
引用
收藏
页码:433 / 440
页数:8
相关论文