Ligand-controlled formation of a low-valent pincer rhodium(I)-dioxygen adduct bearing a very short O-O bond

被引：39

作者：

Frech, Christian M.

Shimon, Linda J. W.

Milstein, David ^{[1
]}

机构：

[1] Weizmann Inst Sci, Dept Organ Chem, IL-76100 Rehovot, Israel

[2] Weizmann Inst Sci, Unit Chem Res Support, IL-76100 Rehovot, Israel

[3] Univ Zurich, Dept Inorgan Chem, CH-8057 Zurich, Switzerland

来源：

HELVETICA CHIMICA ACTA | 2006年 / 89卷 / 08期

关键词：

D O I：

10.1002/hlca.200690170

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Treatment of [{Me2C6H((CH2PBu2)-Bu-t)(2)}Rh(eta(1)-N-2)] (1a) with molecular oxygen (O-2) resulted in almost quantitative formation of the dioxygen adduct [{Me2C6H((CH2PBu2)-Bu-t)(2)}Rh(eta(2)-O-2)] (2a). An X-ray diffraction study of 2a revealed the shortest O-O bond reported for Rh-O-2 complexes, indicating the formation of a Rh-1-O-2 adduct, rather than a cyclic Rh-III eta(2)-peroxo complex. The coordination of the O-2 ligand in 2a was shown to be reversible. Treatment of 2a with CO gas yielded almost quantitatively the corresponding carbonyl complex [{Me2C6H((CH2PBu2)-Bu-t)(2)}Rh(CO)] (3a). Surprisingly, treatment of the structurally very similar pincer complex [{C6H3((CH2PPr2)-Pr-i)(2))}Rh(eta(1)-N-2)] (1b) with O-2 led to partial decomposition, with no dioxygen adduct being observed.

引用

页码：1730 / 1739

页数：10

共 95 条

[1] Synthesis, solution and crystal structures of dinuclear vanadium(V) oxo monoperoxo complexes with mandelic acid:: (NR4)2[V2O2(O2)2(mand)2]•xH2O [R=H,Me,Et; mand=mandelato(2-)=C8H6O32-] [J].