无机化学学报
無機化學學報
무궤화학학보
JOURNAL OF INORGANIC CHEMISTRY
2002年
4期
351-356
,共6页
关敏%刘树堂%吴秉芳%于世泳
關敏%劉樹堂%吳秉芳%于世泳
관민%류수당%오병방%우세영
钴羰基硫簇合物%合成%晶体结构
鈷羰基硫簇閤物%閤成%晶體結構
고탄기류족합물%합성%정체결구
用Co2(CO)8分别与两个杂环配体C(S)NHP(S) (C6H4OCH3)OC(Ph)CH (L1)和C(S)NHC(CH3)2P(S) (CI)N(Ph) (L2)反应.合成两个新的三核钴羰基硫簇合物Co3(CO)7(μ3-S) [μ,η2-CNP(S) (C6H4OCH3)OC(Ph)CH] (Ⅰ)和Co3(CO)7(μ3-S) [μ,η2-SCNC(CH3)2P(S) (CI) N(Ph)] (Ⅱ).用元素分析,IR,1H NMR,31P NMR 及 MS谱表征了它们的结构,同时用X射线衍射法测定了它们的晶体分子结构,二者属于三斜晶系,P1空间群,I的晶胞参数为:a=0.84768(1)nm,b=1.19049(3)nm,c=1.43639(1)nm,α=86.926(1)°,β=81.60l(3)°,γ=88.535(2)°,V=1.4318(5)nm3,Z=2,Dc=1.641g@em-3,F(000)=716,μ=1.893mm-1,R=0.0602,Rw=0.1515.Ⅱ的晶胞参数为:a=1.2050(2)nm,b=1.2448(2)nm,c=0.8951(2)nm,α=97.49(1)°,β=93.552(4)°,γ=108.432(3)°,V=1.2554(3)nm3,Z=2,Dc=1.84lg@cm-3,F(000)=690,μ=2.419mm-1,R=0.0423,Rw=0.1075.Ⅰ和Ⅱ的分子骨架Co3S为三角锥构型,S作为面桥基配体,所有C0作为端基配体与三个Co原子成键.I中含有CoCoCN四元环组件,Ⅱ中含有CoCoSCN五元环组件.
用Co2(CO)8分彆與兩箇雜環配體C(S)NHP(S) (C6H4OCH3)OC(Ph)CH (L1)和C(S)NHC(CH3)2P(S) (CI)N(Ph) (L2)反應.閤成兩箇新的三覈鈷羰基硫簇閤物Co3(CO)7(μ3-S) [μ,η2-CNP(S) (C6H4OCH3)OC(Ph)CH] (Ⅰ)和Co3(CO)7(μ3-S) [μ,η2-SCNC(CH3)2P(S) (CI) N(Ph)] (Ⅱ).用元素分析,IR,1H NMR,31P NMR 及 MS譜錶徵瞭它們的結構,同時用X射線衍射法測定瞭它們的晶體分子結構,二者屬于三斜晶繫,P1空間群,I的晶胞參數為:a=0.84768(1)nm,b=1.19049(3)nm,c=1.43639(1)nm,α=86.926(1)°,β=81.60l(3)°,γ=88.535(2)°,V=1.4318(5)nm3,Z=2,Dc=1.641g@em-3,F(000)=716,μ=1.893mm-1,R=0.0602,Rw=0.1515.Ⅱ的晶胞參數為:a=1.2050(2)nm,b=1.2448(2)nm,c=0.8951(2)nm,α=97.49(1)°,β=93.552(4)°,γ=108.432(3)°,V=1.2554(3)nm3,Z=2,Dc=1.84lg@cm-3,F(000)=690,μ=2.419mm-1,R=0.0423,Rw=0.1075.Ⅰ和Ⅱ的分子骨架Co3S為三角錐構型,S作為麵橋基配體,所有C0作為耑基配體與三箇Co原子成鍵.I中含有CoCoCN四元環組件,Ⅱ中含有CoCoSCN五元環組件.
용Co2(CO)8분별여량개잡배배체C(S)NHP(S) (C6H4OCH3)OC(Ph)CH (L1)화C(S)NHC(CH3)2P(S) (CI)N(Ph) (L2)반응.합성량개신적삼핵고탄기류족합물Co3(CO)7(μ3-S) [μ,η2-CNP(S) (C6H4OCH3)OC(Ph)CH] (Ⅰ)화Co3(CO)7(μ3-S) [μ,η2-SCNC(CH3)2P(S) (CI) N(Ph)] (Ⅱ).용원소분석,IR,1H NMR,31P NMR 급 MS보표정료타문적결구,동시용X사선연사법측정료타문적정체분자결구,이자속우삼사정계,P1공간군,I적정포삼수위:a=0.84768(1)nm,b=1.19049(3)nm,c=1.43639(1)nm,α=86.926(1)°,β=81.60l(3)°,γ=88.535(2)°,V=1.4318(5)nm3,Z=2,Dc=1.641g@em-3,F(000)=716,μ=1.893mm-1,R=0.0602,Rw=0.1515.Ⅱ적정포삼수위:a=1.2050(2)nm,b=1.2448(2)nm,c=0.8951(2)nm,α=97.49(1)°,β=93.552(4)°,γ=108.432(3)°,V=1.2554(3)nm3,Z=2,Dc=1.84lg@cm-3,F(000)=690,μ=2.419mm-1,R=0.0423,Rw=0.1075.Ⅰ화Ⅱ적분자골가Co3S위삼각추구형,S작위면교기배체,소유C0작위단기배체여삼개Co원자성건.I중함유CoCoCN사원배조건,Ⅱ중함유CoCoSCN오원배조건.