Department of Chemistry, 6-355, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA.
Chem Commun (Camb). 2012 Oct 4;48(76):9474-6. doi: 10.1039/c2cc34691e.
The two-electron mixed-valent complex Rh(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)Cl(2) (tfepma = CH(3)NP(OCH(2)CF(3))(2)) photocatalytically splits HCl to generate H(2). Whereas this catalyst degrades rapidly, with H(2) production ceasing after about 36 hours (3 turnovers), a modified complex, Rh(2)(0,II)(tfepma)(2)(CNAd)(2)Cl(2) (CNAd = 1-adamantylisocyanide) displays enhanced stability with sustained H(2) production continuing for >144 h (7 turnovers).
二电子混合价态配合物 Rh(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)Cl(2)（tfepma = CH(3)NP(OCH(2)CF(3))(2)) 光催化分解 HCl 生成 H(2)。尽管该催化剂降解迅速，大约 36 小时（3 个循环）后 H(2)生成停止，但经过修饰的配合物 Rh(2)(0,II)(tfepma)(2)(CNAd)(2)Cl(2)（CNAd = 1-金刚烷基异氰化物）具有增强的稳定性，可持续产生 H(2)超过 144 小时（7 个循环）。
