Syntheses, Structures, and Reactivity of Diruthenium Phosphine Carbonyl Complexes of Nitrites and Nitrates
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- 作者：Kom-Bei Shiu ; Luh-Tin Yang ; Shih-Wei Jean ; Chien-Hsing Li ; Ru-Rong Wu ; Ju-Chun Wang ; Lin-Shu Liou ; and Michael Y. Chiang
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：December 18, 1996
- 年：1996
- 卷：35
- 期：26
- 页码：7845 - 7849
- 全文大小：233K
- 年卷期：v.35,no.26(December 18, 1996)
- ISSN：1520-510X
文摘
A series of diruthenium phosphine carbonyl complexescontaining bridging nitro and nitrato groups,[Ru2(CO)4(
-NO2)2L2](1-4) and[Ru2(CO)4(-NO3)2L2](5-9), were cleanly prepared from the reactionsof [Ru2(CO)4(NCMe)4L2][BF4]2(L = PPh3, PPh2(allyl),PPh2Me, PPhMe2, or PMe3) withexcess NaNO2 or NaNO3 in MeOH.Complexes 1-4 are present in two isomericforms, A and B, with a head-to-head orientationof two bridging
2-(N,O)-NO2 groups forform A and a head-to-tail arrangement of the groups for formB, in an approximate 3:1ratio, but complexes 5-9 are present in onlyone isomeric form with an2-(O,O)-NO3attachment. Crystal data:1A, a = 12.452(2) Å, b =23.520(3) Å, c = 13.441(2) Å, 
=98.280(1)
, monoclinic P21/n,Z = 4; 5, a =11.737(3) Å, b = 23.496(5) Å, c =14.629(3) Å, = 100.34(2), monoclinicP21/n, Z = 4. Thefive-memberedmetallacycle {Ru2(ONO)} in5-9 is more reactive than the four-memberedmetallacycle {Ru2(NO)} in1-4,reflected by the different reactivity of[Ru2(CO)4(-NO2)2(PPh3)2](1) and[Ru2(CO)4(-NO3)2(PPh3)2](5) withvarious reagents to give[Ru2(CO)4(-I)2(PPh3)2](10),[Ru2(CO)4(-N3)2(PPh3)2](11), and[Ru2(CO)4(1-NO3)2(-X)2(PPh3)2] (X = Br(12), I (13)). Crystal data of13: a = 31.394(3) Å, b =9.761(1) Å, c = 18.200(2) Å, = 118.420(1), monoclinic C2/c,Z = 4. The intermolecular oxygen transfer from theligated NO2 groups in1 to exogenous PMe3 is readily observed in MeCNat ambient temperature, apparently forming nitrosyl groupsand free OPMe3.
-NO2)2L2](1-4) and[Ru2(CO)4(-NO3)2L2](5-9), were cleanly prepared from the reactionsof [Ru2(CO)4(NCMe)4L2][BF4]2(L = PPh3, PPh2(allyl),PPh2Me, PPhMe2, or PMe3) withexcess NaNO2 or NaNO3 in MeOH.Complexes 1-4 are present in two isomericforms, A and B, with a head-to-head orientationof two bridging2-(N,O)-NO2 groups forform A and a head-to-tail arrangement of the groups for formB, in an approximate 3:1ratio, but complexes 5-9 are present in onlyone isomeric form with an2-(O,O)-NO3attachment. Crystal data:1A, a = 12.452(2) Å, b =23.520(3) Å, c = 13.441(2) Å, =98.280(1), monoclinic P21/n,Z = 4; 5, a =11.737(3) Å, b = 23.496(5) Å, c =14.629(3) Å, = 100.34(2), monoclinicP21/n, Z = 4. Thefive-memberedmetallacycle {Ru2(ONO)} in5-9 is more reactive than the four-memberedmetallacycle {Ru2(NO)} in1-4,reflected by the different reactivity of[Ru2(CO)4(-NO2)2(PPh3)2](1) and[Ru2(CO)4(-NO3)2(PPh3)2](5) withvarious reagents to give[Ru2(CO)4(-I)2(PPh3)2](10),[Ru2(CO)4(-N3)2(PPh3)2](11), and[Ru2(CO)4(1-NO3)2(-X)2(PPh3)2] (X = Br(12), I (13)). Crystal data of13: a = 31.394(3) Å, b =9.761(1) Å, c = 18.200(2) Å, = 118.420(1), monoclinic C2/c,Z = 4. The intermolecular oxygen transfer from theligated NO2 groups in1 to exogenous PMe3 is readily observed in MeCNat ambient temperature, apparently forming nitrosyl groupsand free OPMe3.