Characterization of Five-Coordinate Ruthenium(II) Phosphine Complexes by X-ray Diffraction and Solid-State 31P CP/MAS NMR Studies and Their Reactivity with Sulfoxides and Thioethers

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• 作者：Kenneth S. MacFarlane ; Ajey M. Joshi ; Steven J. Rettig ; and Brian R. James
• 刊名：Inorganic Chemistry
• 出版年：1996
• 出版时间：December 4, 1996
• 年：1996
• 卷：35
• 期：25
• 页码：7304 - 7310
• 全文大小：201K
• 年卷期：v.35,no.25(December 4, 1996)
• ISSN：1520-510X

文摘

<SUP>31P CP/MAS NMR spectroscopy is examined as a method ofcharacterization for ruthenium(II) phosphinecomplexesin the solid state, and the results are compared with X-raycrystallographic data determined forRuCl₂(dppb)(PPh₃)(dppb =Ph₂P(CH₂)₄PPh₂),RuBr₂(PPh₃)₃, and thepreviously determinedRuCl₂(PPh₃)₃. Crystals ofRuBr₂(PPh₃)₃(C₅₄H₄₅Br₂P₃Ru)are monoclinic, space group P2₁/a,with a = 12.482(4) Å, b =20.206(6) Å, c = 17.956(3) Å,s/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 90.40(2)s/entities/deg.gif">, and Z = 4, and those ofRuCl₂(dppb)(PPh₃)(C₄₆H₄₃Cl₂P₃Ru)are also monoclinic, space groupP2₁/n, with a =10.885(2) Å, b = 20.477(1) Å, c =18.292(2) Å, s/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 99.979(9)s/entities/deg.gif">, and Z = 4.The structure ofRuBr₂(PPh₃)₃ was solved bydirect methods, and that ofRuCl₂(dppb)(PPh₃) was solved bythe Patterson method.The structures were refined by full-matrix least-squaresprocedures to R = 0.048 and 0.031(R_w = 0.046 and0.032) for 5069 and 5925 reflections with I s/entities/ge.gif">3s/gifchars/sigma.gif" BORDER=0 >(I), respectively. Synthetic routes toRuBr₂(dppb)(PPh₃) and[RuBr(dppb)]₂(s/entities/mgr.gif">₂-dppb) arereported. The reactivity ofRuCl₂(dppb)(PPh₃) with the neutraltwo-electron donorligands (L) dimethyl sulfoxide, tetramethylene sulfoxide,tetrahydrothiophene, and dimethyl sulfide to give[(L)(dppb)Ru(s/entities/mgr.gif">-Cl)₃RuCl(dppb)] isdiscussed.