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Issue 9, 2007
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sp Carbon chains surrounded by sp3 carbon double helices: wire-like Pt(C[triple bond, length as m-dash]C)nPt moieties that are spanned by two α,ω-diphosphines that bear heteroatoms or alkyl substituents

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Abstract

Reactions of trans-(C6F5)L2PtCl (2, L = Ph2P(CH2)4O(CH2)2CH[double bond, length as m-dash]CH2; 6, L = Ph2P(CH2)2C(CH3)2(CH2)3CH[double bond, length as m-dash]CH2) and H(C[triple bond, length as m-dash]C)2H (HNEt2, cat. CuI) give trans-(C6F5)L2Pt(C[triple bond, length as m-dash]C)2H (3, 7; 86–97%). Oxidative homocouplings (O2, cat. CuCl/TMEDA, acetone) yield trans,trans-(C6F5)L2Pt(C[triple bond, length as m-dash]C)4PtL2(C6F5) (4, 8; 75–86%). Reactions with Grubbs’ catalyst, followed by hydrogenation, give mainly trans,trans-(C6F5)(Ph2[upper bond 1 start]P(CH2)4O(CH2)6O(CH2)4PPh2)[lower bond 1 start]Pt(C[triple bond, length as m-dash]C)4Pt[upper bond 1 end](Ph2P(CH2)4O(CH2)6O(CH2)4P[lower bond 1 end]Ph2)(C6F5) (5), with termini-spanning diphosphines, and trans,trans-(C6F5)(Ph2[upper bond 1 start]P(CH2)2C(CH3)2(CH2)8C(CH3)2(CH2)2PPh2)Pt[upper bond 1 end](C[triple bond, length as m-dash]C)4[upper bond 1 start]Pt(Ph2P(CH2)2C(CH3)2(CH2)8C(CH3)2(CH2)2P[upper bond 1 end]Ph2)(C6F5) (9), with trans-spanning diphosphines, respectively. Reactions of trans,trans-(C6F5)(p-tol3P)2Pt(C[triple bond, length as m-dash]C)4Pt(Pp-tol3)2(C6F5) with Ph2P(CH2)2C(CH3)2(CH2)8C(CH3)2(CH2)2PPh2 and p-tol2P(CH2)3(CF2)8(CH2)3Pp-tol2 give 10 (70%), the isomer of 9 with termini-spanning diphosphines, and the analogous adduct of the fluorinated diphosphine. However, the latter oligomerizes upon attempted workup. The crystal structure of 5 shows that the sp3 chains adopt a chiral double-helical conformation about the sp chain, with the endgroups defining a 164.1° angle. Additional conformational properties of the preceding complexes are analyzed in detail, and dynamic properties are probed by low temperature NMR experiments.

Graphical abstract: sp Carbon chains surrounded by sp3 carbon double helices: wire-like Pt(C [[triple bond, length as m-dash]] C)nPt moieties that are spanned by two α,ω-diphosphines that bear heteroatoms or alkyl substituents

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Publication details

The article was received on 07 Jun 2007, accepted on 06 Jul 2007 and first published on 10 Aug 2007


Article type: Paper
DOI: 10.1039/B708690N
New J. Chem., 2007,31, 1594-1604

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    sp Carbon chains surrounded by sp3 carbon double helices: wire-like Pt(C[triple bond, length as m-dash]C)nPt moieties that are spanned by two α,ω-diphosphines that bear heteroatoms or alkyl substituents

    L. de Quadras, E. B. Bauer, J. Stahl, F. Zhuravlev, F. Hampel and J. A. Gladysz, New J. Chem., 2007, 31, 1594
    DOI: 10.1039/B708690N

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