二苯基磷硫代甲酸根配位基鉬金屬錯化物的合成與反應性探討

將化合物[Et_4N][Mo(CO)_5(PPh_2)](1)與二硫化碳作用可得到錯合物[Et_4N][Mo(CO)_5(PPh_2CS_2)](3)，其中錯合物3亦可經由配位基[Et_4N][(PPh_2CS_2)](2)與錯化物Mo(CO)_5(CH_3CN）作用而獲得。於錯合物3中，二苯基磷硫代甲酸根配位基，PPh_2CS_(2-)，是以磷原子與金屬鍵結。錯合物3與不同的鹵烷類作用可得到中性的錯合物MO(CO)_5[(PPh_2CS_2R)](R=C_2H_5,C_2H_4OH,C_3H_5,4-6)。醯化作用中，錯化物3與1-義萘CO_10H_7C(O)Cl作用可得到低產率的錯化物Mo(CO)_5[(PPh_2CS_2COC_10H_7)](7)，烷化與醯化作用皆發生於錯化物的硫原子上。錯化物3與二碘甲烷作用，可得到一個雙金屬錯合物〔Mo(CO)_5(PPh_2CS_2)〕_2：（μ-CH_2)(8)，其中的兩個金屬是以兩個磷的雙芽配位基為架橋而連結。錯化物3的去羰基反應可於乙腈溶劑中進行，獲得一個離子性錯合物[Et_4N][Mo(CO)_4(PPh_2CS_2)](9)。錯合物9中的二苯基磷硫代甲酸根配位基，PPh_2CS_(2-)，是以磷及一個硫原子與金屬鍵結。所有錯合物皆經由光譜學方法鑑定而知。

關鍵字

二苯基磷硫代甲酸根配位基；鉬金屬錯化合物

並列摘要

Treatment of [Et_4N][Mo(CO)_5(PPh_2)] (1) with CS_2 afforded [Et_4N][Mo(CO)_5(PPh_2CS_2)] (3) which was also synthesized from the reaction of Mo(CO)_5(CH_3CN) with [Et_4N][PPh_2CS_2] (2). In complex 3, the diphenylphosphinodithioformato ligand, PPh_2CS_(2-), coordinated to the molybdenum through the phosphorus atom. The reactions of 3 with various alkyl halides yielded the neutral complexes Mo(CO)_5[PPh_2(CS_2R)] (R = C_2H_5, C_2H_4OH, C_3H_5, 4-6). Acylation of 3 with 1-Naphthoyl chloride [C_10H_7C(O)Cl] gave complex Mo(CO)_5[PPh_2(CS_2COC_10H_7)] (7) with low yield. Alkylation and acylation reactions occurred at the sulfur atom. Complex 3 reacted with CH_2l_2 to give the dinuclear complex [Mo(CO)_5(PPh_2CS_2)]_ 2(μ-CH_2) (8) in which the two metal atoms are bridged by the bidentate phosphorus ligand. Decarbonylation of 3 in CH_3CN produced an anionic product which was identified as [Et_4N][Mo(CO)_4(PPh_2CS_2,)] (9). The PPh_2CS_(2-) ligand of 9 bound to the metal center through both the phosphorus and one of the sulfur atoms. All of the complexes are identified by spectroscopic methods.