The ortho-benzyne diradical, o-C(6)H(4) has been produced with a supersonic nozzle and its subsequent thermal decomposition has been studied. As the temperature of the nozzle is increased, the benzyne molecule fragments: o-C(6)H(4)+Delta--> products. The thermal dissociation products were identified by three experimental methods: (i) time-of-flight photoionization mass spectrometry, (ii) matrix...

The coordination properties of the beta-keto phosphine ligands R(2)PCH(2)C(O)Ph (, R = i-Pr; , R = Ph), of the new acetamide-derived phosphine ligand (i-Pr)(2)PNHC(O)Me () and of Ph(2)PNHC(O)Me () have been examined towards Ni(ii) complexes. Comparisons are made between systems in which the PCH(2) function of the ketophosphine has been replaced with an isoelectronic PNH group in amide-derived l...

The ion radicals of two series of platinum acetylide oligomers have been subjected to study by electrochemical and pulse radiolysis/transient absorption methods. One series of oligomers, Ptn, has the general structure Ph-C[triple bond]C-[Pt(PBu3)2-C[triple bond]C-(1,4-Ph)-C[triple bond]C-]n-Pt(PBu3)2-C[triple bond]C-Ph (where x=0-4, Ph=phenyl and 1,4-Ph=1,4-phenylene). The second series of olig...

The new conjugated organometallic polymer (-spacer-C[triple bond]C-Pt(PBu3)2-C[triple bond]C-)n (3; spacer = para-bis(diphenyl(tetramethyl)quinone diimine) and the cyclic mononuclear model complex, spacer'-C[triple bond]C-Pt(PEt3)2-C[triple bond]C x CuCl (4; spacer' = ortho-diphenyl-2,3,5,6-tetramethyl-1,4-benzoquinone diimine) were synthesized from the 1:1 condensation of the corresponding die...

A series of homoleptic and heteroleptic platinum(II) complexes [Pt(C[triple bond]CFc)2(L-L)] (L-L = COD 1, 1,1'-bis(diphenylphosphino)ferrocene (dppf) 2), Q2[cis/trans-Pt(C6F5)2(C[triple bond]CFc)2] (cis, Q = PMePh3, 3; trans, Q = NBu4, 4), (NBu4)[Pt(bzq)(C[triple bond]CFc)2] 5 (Hbzq = 7,8-benzoquinoline) and (NBu4)2[Pt(C[triple bond]CFc)4] 6 has been synthesized and characterized spectroscopic...

We have produced and investigated an unique boron oxide cluster, B4O2(-), using photoelectron spectroscopy and ab initio calculations. Relatively simple and highly vibrationally resolved PES spectra were obtained at two photon energies (355 and 193 nm). The electron affinity of neutral B4O2 was measured to be 3.160 +/- 0.015 eV. Two excited states were observed for B4O2 at excitation energies o...

trans-[Pt(C[triple bond]C(Ar)C[triple bond]CH)2(PMe3)2](Ar = C(6)Me(4)-3,4,5,6) (1) reacts with PPN[Au(acac)(2)](Hacac = acetylacetone; 1 : 1.16 molar ratio; PPN = (Ph3P)2N) to give PPN[(Au[Pt(PMe3)2]2)(mu-Ar(C[triple bond]C)2)3] (2) the crystal structure of which showed the anions as quasi equilateral triangles stacked parallel to each other through C-HAu interactions, resulting in channels of...

Incorporation of diplatinum complex Pt2(micro-dppm)2(bpyC[triple bond]C)4 or Pt2(mu-dppm)2(phenC[triple bond]C)4 with Ln(hfac)3(H2O)2 (Ln = Nd, Eu, Yb) gave a series of Pt2Ln2 and Pt2Ln4 bimetallic arrays, in which the excitation of d(Pt) -->pi*(R-C[triple bond]C) MLCT absorption induces sensitisation of lanthanide luminescence through efficient d --> f energy transfer from Pt(II) alkynyl chrom...

Transition metal reagents and catalysts are generally effective to cleave all three bonds (one σ and two π) in a triple bond despite its high bonding energy. Recently, chemistry of single-bond cleavage by using main-group element compounds is rapidly being developed in the absence of transition metals. However, the cleavage of a triple bond using non-transition-metal compounds is less explored....

Two conjugated organometallic oligomers of the type (-C[triple bond]CPt(L)(2)C[triple bond]C(ZnP)-)(n) and model compounds [PhC[triple bond]CPt(L)(2)C[triple bond]C(ZnP)C[triple bond]CPt(L)(2)C[triple bond]CPh] with L = tri(n-butyl)-phosphine and ZnP = zinc(II)(10,20-bis(Ar)porphyrine) (Ar = mesityl (Mes; P1 and M1) or 3,4,5-trihexadecyloxyphenyl (P2 and M2)) were synthesized and characterized ...