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Issue 87, 2018
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Alkynylbis(alkylidynyl)phosphines: {LnM[triple bond, length as m-dash]C}2PC[triple bond, length as m-dash]CR

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Abstract

Sequential treatment of [M([triple bond, length as m-dash]CBr)(CO)2(Tp*)] (M = Mo, W; Tp* = hydrotris(dimethylpyrazolyl)borate) with nBuLi, RPCl2 and LiC[triple bond, length as m-dash]CSiMe3 affords [M{[triple bond, length as m-dash]CPR(C[triple bond, length as m-dash]CSiMe3)}(CO)2(Tp*)] (R = Ph, Cy) which are readily desilylated (TBAF) to provide the parent ethynyl derivatives [M{[triple bond, length as m-dash]CPR(C[triple bond, length as m-dash]CH)}(CO)2(Tp*)]. Alternatively, treating [W([triple bond, length as m-dash]CBr)(CO)2(Tp*)] with nBuLi, 1/2 PCl3 and LiC[triple bond, length as m-dash]CR′ affords the alkynylbis(alkylidynyl)phosphines [R′C[triple bond, length as m-dash]CP{C[triple bond, length as m-dash]W(CO)2(Tp*)}2] (R′ = C6H5, C6H4Me-4, CMe3, SiMe3) and again the silyl derivative may be desilylated to the parent (R′ = H) which is readily converted to an arsino derivative (R′ = AsPh2). These novel architectures present new linkages for bridge-assisted polymetallic assembly.

Graphical abstract: Alkynylbis(alkylidynyl)phosphines: {LnM [[triple bond, length as m-dash]] C}2PC [[triple bond, length as m-dash]] CR

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Publication details

The article was received on 04 Sep 2018, accepted on 11 Oct 2018 and first published on 11 Oct 2018


Article type: Communication
DOI: 10.1039/C8CC07166G
Citation: Chem. Commun., 2018,54, 12373-12376

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    Alkynylbis(alkylidynyl)phosphines: {LnM[triple bond, length as m-dash]C}2PC[triple bond, length as m-dash]CR

    B. J. Frogley and A. F. Hill, Chem. Commun., 2018, 54, 12373
    DOI: 10.1039/C8CC07166G

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