Alkynyldiphenylphosphine d8 (Pt, Rh, Ir) Complexes: Contrasting Behavior toward cis-[Pt(C6F5)2(THF)2]
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- 作者：Jesú ; s R. Berenguer ; Marí ; a Bernechea ; Juan Fornié ; s ; Ana Garcí ; a ; Elena Lalinde ; and M. Teresa Moreno
- 刊名：Inorganic Chemistry
- 出版年：2004
- 出版时间：December 13, 2004
- 年：2004
- 卷：43
- 期：25
- 页码：8185 - 8198
- 全文大小：318K
- 年卷期：v.43,no.25(December 13, 2004)
- ISSN：1520-510X
文摘
The synthesis and characterization of a series of mononuclear d8 complexes with at least two P-coordinatedalkynylphosphine ligands and their reactivity toward cis-[Pt(C6F5)2(THF)2] are reported. The cationic [Pt(C6F5)(PPh2C
f">CPh)3](CF3SO3), 1, [M(COD)(PPh2Cf">CPh)2](ClO4) (M = Rh, 2, and Ir, 3), and neutral [Pt(o-C6H4E2)(PPh2Cf">CPh)2] (E = O, 6, and S, 7) complexes have been prepared, and the crystal structures of 1, 2, and7·CH3COCH3 have been determined by X-ray crystallography. The course of the reactions of the mononuclearcomplexes 1-3, 6, and 7 with cis-[Pt(C6F5)2(THF)2] is strongly influenced by the metal and the ligands. Thus,treatment of 1 with 1 equiv of cis-[Pt(C6F5)2(THF)2] gives the double inserted cationic product [Pt(C6F5)(S)
f">-{C(Ph)=C(PPh2)C(PPh2)=C(Ph)(C6F5)}Pt(C6F5)(PPh2Cf">CPh)](CF3SO3) (S = THF, H2O), 8 (S = H2O, X-ray), whichevolves in solution to the mononuclear complex [(C6F5)(PPh2Cf">CPh)Pt{C10H4-1-C6F5-4-Ph-2,3-
fchars/kappa.gif" BORDER=0 >PP'(PPh2)2}](CF3SO3), 9 (X-ray), containing a 1-pentafluorophenyl-2,3-bis(diphenylphosphine)-4-phenylnaphthalene ligand, formedby annulation of a phenyl group and loss of the Pt(C6F5) unit. However, analogous reactions using 2 or 3 asprecursors afford mixtures of complexes, from which we have characterized by X-ray crystallography thealkynylphosphine oxide compound [(C6F5)2Pt(f">-fchars/kappa.gif" BORDER=0 >O:fchars/eta.gif" BORDER=0 >2-PPh2(O)Cf">CPh)]2, 10, in the reaction with the iridium complex(3). Complexes 6 and 7, which contain additional potential bridging donor atoms (O, S), react with cis-[Pt(C6F5)2(THF)2] in the appropriate molar ratio (1:1 or 1:2) to give homo- bi- or trinuclear [Pt(PPh2Cf">CPh)(f">-fchars/kappa.gif" BORDER=0 >E-o-C6H4E2)(f">-fchars/kappa.gif" BORDER=0 >P:fchars/eta.gif" BORDER=0 >2-PPh2Cf">CPh)Pt(C6F5)2] (E = O, 11, and S, 12) and [{Pt(f">3-fchars/kappa.gif" BORDER=0 >2EE'-o-C6H4E2)(f">-fchars/kappa.gif" BORDER=0 >P:fchars/eta.gif" BORDER=0 >2-PPh2Cf">CPh)2}{Pt(C6F5)2}2] (E = O, 13, and S, 14) complexes. The molecular structure of 14 has been confirmed byX-ray diffraction, and the cyclic voltammetric behavior of precursor complexes 6 and 7 and polymetallic derivatives11-14 has been examined.
f">CPh)3](CF3SO3), 1, [M(COD)(PPh2Cf">CPh)2](ClO4) (M = Rh, 2, and Ir, 3), and neutral [Pt(o-C6H4E2)(PPh2Cf">CPh)2] (E = O, 6, and S, 7) complexes have been prepared, and the crystal structures of 1, 2, and7·CH3COCH3 have been determined by X-ray crystallography. The course of the reactions of the mononuclearcomplexes 1-3, 6, and 7 with cis-[Pt(C6F5)2(THF)2] is strongly influenced by the metal and the ligands. Thus,treatment of 1 with 1 equiv of cis-[Pt(C6F5)2(THF)2] gives the double inserted cationic product [Pt(C6F5)(S)f">-{C(Ph)=C(PPh2)C(PPh2)=C(Ph)(C6F5)}Pt(C6F5)(PPh2Cf">CPh)](CF3SO3) (S = THF, H2O), 8 (S = H2O, X-ray), whichevolves in solution to the mononuclear complex [(C6F5)(PPh2Cf">CPh)Pt{C10H4-1-C6F5-4-Ph-2,3-fchars/kappa.gif" BORDER=0 >PP'(PPh2)2}](CF3SO3), 9 (X-ray), containing a 1-pentafluorophenyl-2,3-bis(diphenylphosphine)-4-phenylnaphthalene ligand, formedby annulation of a phenyl group and loss of the Pt(C6F5) unit. However, analogous reactions using 2 or 3 asprecursors afford mixtures of complexes, from which we have characterized by X-ray crystallography thealkynylphosphine oxide compound [(C6F5)2Pt(f">-fchars/kappa.gif" BORDER=0 >O:fchars/eta.gif" BORDER=0 >2-PPh2(O)Cf">CPh)]2, 10, in the reaction with the iridium complex(3). Complexes 6 and 7, which contain additional potential bridging donor atoms (O, S), react with cis-[Pt(C6F5)2(THF)2] in the appropriate molar ratio (1:1 or 1:2) to give homo- bi- or trinuclear [Pt(PPh2Cf">CPh)(f">-fchars/kappa.gif" BORDER=0 >E-o-C6H4E2)(f">-fchars/kappa.gif" BORDER=0 >P:fchars/eta.gif" BORDER=0 >2-PPh2Cf">CPh)Pt(C6F5)2] (E = O, 11, and S, 12) and [{Pt(f">3-fchars/kappa.gif" BORDER=0 >2EE'-o-C6H4E2)(f">-fchars/kappa.gif" BORDER=0 >P:fchars/eta.gif" BORDER=0 >2-PPh2Cf">CPh)2}{Pt(C6F5)2}2] (E = O, 13, and S, 14) complexes. The molecular structure of 14 has been confirmed byX-ray diffraction, and the cyclic voltammetric behavior of precursor complexes 6 and 7 and polymetallic derivatives11-14 has been examined.