A hemilabile binucleating pincer ligand for self-assembly of coordination oligomers and polymers

作者：Zhao Chang Qiu; Jennings Michael C; Puddephatt Richard J^*

来源：Dalton Transactions, 2008, (9): 1243-1250.

DOI：10.1039/b716035f

The bis(PNP)-donor pincer ligand 1,4-C6H4{N(CH2CH2PPh2)(2)}(2), 1, contains weakly basic nitrogen donor atoms because the lone pairs of electrons are conjugated to the bridging phenylene group, and this feature is used in the synthesis of oligomers and polymers. The complexes [Pd2X2(mu-1)](OTf)(2), X = Cl, Br or OTf, contain the ligand 1 in bis(pincer) binding mode (mu-kappa(6)-P4N2), but [Pd4Cl6(mu(3-)1)(2)]Cl-2 contains the ligand in an unusual unsymmetrical mu(3)-kappa(5)-P4N binding mode. The bromide complex is suggested to exist as a polymer [{Pd(2)B(r)4(mu(4)-1)}(n)] with the ligands 1 in mu(4)-kappa(4)-P-4 binding mode. The methylplatinum(II) complexes [Pt2Me4(mu-1)] and [Pt2Me2(mu-1)](O2CCF3)(2) contain the ligand 1 in mu-kappa(4)-P-4 and mu-kappa(6)-P4N2 bonding modes, while the silver(I) complex [Ag-2(O2CCF3)(2) (mu-1)] contains the ligand 1 in an intermediate bonding mode in which the nitrogen donors are very weakly coordinated. The complexes [Pd-2(OTf)(2)(mu-1)](OTf)(2) and [Ag-2(O2CCF3)(2)(mu-1)] react with 4,4'-bipyridine to give polymers [Pd-2(mu-bipy)(mu-1)](OTf)(4) and [Ag-2(mu-bipy)(mu-1)](O2CCF3)(2).

• 出版日期2008