Synthesis, Structure, and Reactivity of Ruthenium and Osmium Nitrido Complexes with 1,2-Benzenedithiolate Ligands: N- versus S-Alkylation
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- 作者：Dieter Sellmann ; Michael W. Wemple ; Wolfgang Donaubauer ; and Frank W. Heinemann
- 刊名：Inorganic Chemistry
- 出版年：1997
- 出版时间：March 26, 1997
- 年：1997
- 卷：36
- 期：7
- 页码：1397 - 1402
- 全文大小：175K
- 年卷期：v.36,no.7(March 26, 1997)
- ISSN：1520-510X
文摘
The reactivity of the nitrido complexes(NnBu4)[Ru(N)(S2C6H4)2](1) and(NnBu4)[Os(N)(S2C6H4)2](2) (C6H4(SH)2 = 1,2-benzenedithiol) toward electrophiles,R+ (R = Me, Et, Ph3C), is described.While 1 yielded intractablemixtures of products, 2 could be cleanly alkylated. Thesynthesis of 1 has been reported previously (Z.Naturforsch.1987, 42B, 341); complex 2 can besynthesized by treating(NnBu4)[Os(N)Cl4]with deprotonated 1,2-benzenedithiolin acetone/MeOH at 0 
C. Complexes 1 and 2are isostructural and crystallize in the orthorhombic spacegroupPna21, Z = 8, with a =36.881(6) Å, b = 9.402(2) Å, and c= 17.652(2) Å for 1 and a =37.042(4) Å, b =9.375(2) Å, and c = 17.671(2) Å for2. The anions of both compounds consist of afive-coordinate mononuclearcenter with a distorted square-pyramidal geometry; a terminal nitridoligand occupies the apical position and twochelating(S2C6H4)2-ligands form the basal plane. Treatment of 2 withR3OBF4 inCH2Cl2 yields[Os(N)(S2C6H4)(SC6H4SR)](R = Me, 3; R = Et, 4) where one thiolatedonor is alkylated. Alkylation of thesulfur of the 1,2-benzenedithiolate ligand was confirmed by NMRspectroscopy and X-ray crystallography (for3). Complex3·CH2Cl2 crystallizes inthe orthorhombic space groupP212121, Z= 4, with a = 8.551(1) Å, b=10.772(2) Å, and c = 19.716(3) Å. Incontrast, treatment of 2 withPh3CPF6 inCH2Cl2 yields[Os(NCPh3)(S2C6H4)2](5), whose 1H and 13C NMR spectraindicate that the terminal nitride is the site of electrophilicattack.X-ray crystallography further confirms the alkylation at thenitrogen atom; complex 5 crystallizes in thetriclinicspace group P
, Z = 2, with a= 9.338(8) Å, b = 10.001(3) Å, c= 16.280(6) Å, 
= 75.88(3), 
=74.29(6),and 
= 69.55(5).
C. Complexes 1 and 2are isostructural and crystallize in the orthorhombic spacegroupPna21, Z = 8, with a =36.881(6) Å, b = 9.402(2) Å, and c= 17.652(2) Å for 1 and a =37.042(4) Å, b =9.375(2) Å, and c = 17.671(2) Å for2. The anions of both compounds consist of afive-coordinate mononuclearcenter with a distorted square-pyramidal geometry; a terminal nitridoligand occupies the apical position and twochelating(S2C6H4)2-ligands form the basal plane. Treatment of 2 withR3OBF4 inCH2Cl2 yields[Os(N)(S2C6H4)(SC6H4SR)](R = Me, 3; R = Et, 4) where one thiolatedonor is alkylated. Alkylation of thesulfur of the 1,2-benzenedithiolate ligand was confirmed by NMRspectroscopy and X-ray crystallography (for3). Complex3·CH2Cl2 crystallizes inthe orthorhombic space groupP212121, Z= 4, with a = 8.551(1) Å, b=10.772(2) Å, and c = 19.716(3) Å. Incontrast, treatment of 2 withPh3CPF6 inCH2Cl2 yields[Os(NCPh3)(S2C6H4)2](5), whose 1H and 13C NMR spectraindicate that the terminal nitride is the site of electrophilicattack.X-ray crystallography further confirms the alkylation at thenitrogen atom; complex 5 crystallizes in thetriclinicspace group P, Z = 2, with a= 9.338(8) Å, b = 10.001(3) Å, c= 16.280(6) Å, = 75.88(3), =74.29(6),and = 69.55(5).