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Chemistry of low-valent platinum dimers

Physical and chemical properties of low-valent platinum dimers, 
namely [Pt_2(P_2O_5H_2)4]^(4-) and Pt_2(µ-dppm)_2Cl_2, have been investigated 
using a variety of structural and spectroscopic techniques. Platinum(II) d^8-d^8 dimers have been shown to exhibit much thermal 
and photochemical reactivity. Chapter 2 describes studies aimed at elucidating the excited state reduction potenetial of [Pt_2(P_2O_5H_2)4]^(4-), 
Pt_2, in organic media. By conducting excited state electron transfer 
studies using derivatized pyridiniums and benzophenones, the 
excited state reduction potential has been estimated to be ~2 V. The 
Pt_2 complex undergoes partial oxidation to form Pt(II,III) linear 
chains. Chapter 3 describes the structural and spectroscopic 
techniques used to determine the translational symmetries of these 
[Pt_2(P_2O_5H_2)4]^(4-) (X = Cl, Br), Pt_2X, chains. Pt_2Br has been found to 
be intermediate between (AAB)_n and (AABCCB)_n, while, Pt_2Cl is of 
(AABCCB)_n translational symmetry. Investigations into the electronic 
transitions of Pt_2Cl and Pt_2Br were conducted using high pressure 
techniques and are presented in Chapter 4. The Pt_2X electronic 
spectrum exhibits bands attributable to the reduced Pt2 complex and the 
oxidized Pt_2X_2 complex [Pt_2(P_2O_5H_2)4]^(4-) along with an intervalence 
charge-tranfer band characteristic of a mixed-valence solid. Photophysical investigations of a new luminescent chromophore, 
Pt_2(µ-dppm)_2Cl_2, a d^9-d^9 dimer, and its analogs are described in 
Chapter 5. The absorption band directly responsible for the observed 
emission is believed to be very weak and, as of yet, unobserved. 
Attempts to determine the spin multiplicty and approximate energy of 
this unobserved transition are described in Chapter 6. Excited-state 
energy transfer studies indicate that this absorption band is a triplet 
transition at -13,000 cm^(-1). Although, the Pt_2(µ-dppm)_2Cl_2 excited 
state is non-luminescent in fluid solution, it has been shown to 
undergo thermal electron transfer to tetracyanoethylene and photoinduced 
electron transfer to methylviologen. These experiments are 
presented in Chapter 7. Preliminary studies, described in Chapter 8, 
of non-bridged d^9-d^9 platinum(I) dimers have shown that [Pt_2(CNCH_3)_6]^(2+) 
serves as a versatile precursor in the synthesis of new d^8-d^8 A-frame 
complexes.