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Synthesis, Structures, and Properties of Diiron Azadithiolate Complexes Containing a Subphthalocyanine Moiety as Biomimetic Models for [FeFe]‐Hydrogenases
Author(s) -
Song LiCheng,
Luo FeiXian,
Tan Hao,
Sun XiaoJing,
Xie ZhaoJun,
Song HaiBin
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300038
Subject(s) - chemistry , tetrahydrofuran , yield (engineering) , moiety , toluene , medicinal chemistry , bimetallic strip , stereochemistry , derivative (finance) , catalysis , organic chemistry , materials science , solvent , metallurgy , economics , financial economics
The first two model compounds for [FeFe]‐hydrogenases that contain a subphthalocyanine (SubPc) macrocycle, namely, [{(μ‐SCH 2 ) 2 N(CH 2 ) 2 CO 2 ‐3‐C 6 H 4 S 2 C 6 H 4 ‐3′‐O(SubPc)}Fe 2 (CO) 6 ] ( 5 ) and [{(μ‐SCH 2 ) 2 NC 6 H 4 ‐4‐O(SubPc)}Fe 2 (CO) 6 ] ( 8 ), have been synthesized and structurally characterized. The treatment of chlorosubphthalocyanine (SubPc‐Cl, 1 ) with (3‐HOC 6 H 4 S) 2 in toluene gave the corresponding phenoxy‐substituted SubPc derivative 3‐HOC 6 H 4 S 2 C 6 H 4 ‐3′‐O(SubPc) ( 2 ) in 78 % yield, whereas the reaction of in‐situ‐generated [(μ‐HOCH 2 S) 2 Fe 2 (CO) 6 ] ( 3 ) with β‐alanine afforded diiron complex [{(μ‐CH 2 S) 2 N(CH 2 ) 2 CO 2 H}Fe 2 (CO) 6 ] ( 4 ) in 53 % yield. Further treatment of 2 with 4 in the presence of N , N′ ‐dicyclocarbodiimide (DCC) and N , N ‐dimethyl‐4‐aminopyridine (DMAP) in CH 2 Cl 2 resulted in the formation of model compound 5 in 86 % yield. Model compound 8 could be prepared by two methods. One method involves the reaction of in‐situ‐generated 3 with 4‐aminophenol in tetrahydrofuran (THF) to give diiron complex [{(μ‐CH 2 S) 2 NC 6 H 4 OH‐4}Fe 2 (CO) 6 ] ( 6 ) in 61 % yield and further treatment of SubPc‐Cl ( 1 ) with 6 in toluene to give 8 in 13 % yield. The other method involves the reaction of SubPc‐Cl ( 1 ) with silver triflate (AgOTf) followed by treatment of the resulting intermediate SubPc‐OTf ( 7 ) with 6 in the presence of Et 3 N to produce 8 in a much higher yield (59 %). All the new precursors ( 2 , 4 , and 6 ) and the model compounds 5 and 8 have been fully characterized by elemental analysis and various spectroscopy techniques, as well by X‐ray crystallography for 2 , 4 , 6 , and 8 . In addition, the photoinduced H 2 production catalyzed by model 8 was preliminarily investigated.