Platinum acetylide complexes

When the preparation of the second-generation dendrimer was attempted by reacting trinuclear platinum-acetylide complex (27) (Fig. 5), which is also a first... 

Fig. 6. Tetranuclear platinum-acetylide complex 35 used as the core for convergent synthesis...

Ramakrishna G, Goodson T III, Rogers-Haley JE, Cooper TM, McLean DG, Urbas A (2009) Ultrafast intersystem crossing excited state dynamics of platinum acetylide complexes. J Phys Chem C 113 1060-1066... 

The triple bond can be reduced with hydrazine to form the vinyl complex with a cis stereochemistry about the carbon-carbon double bond (equation 223).617 The five types ol reaction between platinum acetylide complexes and aprotic compounds A—B have beer summarized. These are (a) oxidative addition (A—B is I2, IBr, ICN, Mel etc.) (b) insertior (A—B is C2(CN)4) (c) addition across the triple bond to form vinyl complexes (A—B is CF3COCI, o-tetrachloroquinone, Br, NOC1) (d) insertion into the C—H bond (A—B is (CFs)2CO) and (e) formation of five-coordinate adducts.618... 

To understand the physical meaning of the electronic structures of platinum acetylide complexes, theoretical calculations have been employed to deduce information related to the molecular orbitals and the electronic transitions. The first theoretical... 

One of the most recent works on the electronic structures of platinum acetylide complexes using theoretical calculations was performed by Ding et al [104], In this... 

A series of four platinum acetylide complexes that contain 4-ethynylstilbene (4-ES) ligands have been subjected to a detailed photochemical and photophysical investigation [83]. Using absorption, variable temperature photoluminescence, and transient absorption spectroscopy, UV-vis absorption, and NMR spectroscopy, it was shown that these compounds undergo trans-cis photoisomerization from the triplet excited state. The obtained experimental data indicated that in all of the complexes, excitation led to a high yield of a 3n,n excited state that is localized on... 

For example, in 1963 the photochemistry of magnesium phthalocyanine with coordinated uranium cations was studied in pyridine and ethanol and indicated the occurrence of PET to the uranium complex . A rapid photoinduced electron transfer (2-20 ps) followed by an ultrafast charge recombination was shown for various zinc and magnesium porphyrins linked to a platinum terpyridine acetylide complex . The results indicated the electronic interactions between the porphyrin subunit and the platinum complex, and underscored the potential of the linking para-phenylene bisacetylene bridge to mediate a rapid electron transfer over a long donor-acceptor distance. 

Platinum(II) acetylide complexes are best prepared using Na or K acetylide in liquid ammonia solvent (equation 157).454,455 Sodium dicyanomethanide can also be used to prepare platinum(II) complexes of this anion (equation 158).456... 

Hexafluorobutyne-2 will add to platinum(II) complexes. The insoluble complex PtMe HB(pz)3 reacts with dissolution and the five-coordinate alkyne complexes can be isolated (equation 269).815 The coordination about platinum(II) is essentially trigonal bipyrami-dal. The C C triple bond is lengthened on coordination to 1.292(12) A and the alkyne bend-back angle is 34.4(4)°.816 These complexes have a -bonded alkyne ligand, and show different structural and reaction chemistry than platinum(II) acetylide complexes.817-821... 

In the case of the asymmetrically substituted platinum acetylides, SHG was detected in all samples (Table II). The symmetrically substituted bis(pyridylacetylide) complex 7c was found to be centrosymmetric. Signals were quantified by peak height analysis of several laser pulses. 

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