Platinum 0 state, complexes

Since n bonding is believed to be more important in low oxidation states, as d orbitals contract with increasing oxidation state leading to poorer dw-pw overlap, this would not be expected on the basis of a 7r-bonding mechanism. Similarly, one can compare /(Pt-P) for pairs of isomers in the +2 and +4 states in a planar platinum(II) complex, the platinum 6s orbital is shared by four ligands whereas in an octahedral platinum(IV) complex it is shared by six ligands. Therefore, the 6s character is expected to be only 2/3 as much in the platinum(IV) complexes, correlating well with the 7(Pt-P) values, which can be taken to be a measure of the a-character in the bond. 

Most work on platinum involves complexes in the divalent state. Malatesta and Bonati report no platinum(O) or platinum(IV) species. The lack of... 

For palladium and platinum, dithiocarbamato complexes with the metal in the oxidation state of -H 2 and -i- 4 are known. 

In a study of the hydrolysis of platinum(II)-nitrile complexes to afford the corresponding amides, the first well-characterized examples of platinum(II) complexes that dimerize spontaneously to form weakly bonded Pt-Pt dimers with an unsupported intermetallic bond have been described.166 For example, treatment of cw-[PtCl2(NCBut)2] with excess KOH affords the amide species cw-[PtCl2 HN=C(OH)But 2], which exists as a dimer (49) both in solution and in the solid state, with a Pt-Pt bond length of 3.165(1) A, as determined by X-ray crystallography. Four... 

An extremely rare example of a six-coordinate platinum(II) complex has been prepared by the reaction of [Pt(dmpe)2]2+ with three equivalents of I2 in H20/EtOH solution which affords black crystals of [PtI(dmpe)2(K-I2)]I3 (102). X-ray crystallography reveals a neutral I2 ligand that is coordinated to the metal center through one of the iodine atoms.278 XPS (X-ray photoelectron spectroscopy) measurements are consistent with the platinum center having a +2 oxidation state. 

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... 

Fig. 4. Relevant structures for the discussion of methane activation by (bipyrimi-dine)PtCl2 Methane complex of Pt(II) (A) methyl(hydrido)platinum(IV) complex, the product of the oxidative addition (B) transition state for intramolecular deprotonation of the methane complex ( cr-bond metathesis , sometimes also called electrophilic , C) intermolecular deprotonation of the methane complex ( electrophilic pathway , D).

Since it is known that the tetranuclear mixed-valent platinum-blue complexes such as 19 and 57 undergo disproportionation and reduction by water as Eqs. (1)—(3) and (7)—(9) show (106, 113), all the species appearing in Eqs. (1)—(3) and (7)—(9) are present in the solution. However, only one or several of the four species in the solution may in fact be resposible for the catalytic olefin oxidation. To clarify this point, the effect of the Pt oxidation state in the platinum complexes was compared. The results are summarized in Table VII, which... 

Fig.6 The organo-platinum(II) complex containing N,C,N tridentate ligands reversibly binds gaseous SO2 in the solid state. The reversible reaction occurs at the Pt(ll) complex by Pt-S bond formation and cleavage. Uptake and release of SO2 does not destroy the crystalline ordering... 

Similar to (SN)t in their one-dimenston.il conductivity properties arc the stacked columnar complexes typified by [Pl(CN)j i. These square planar ions adopt a closely spaced parallel arrangement, allowing for considerable interaction among the d i orbitals of the platinum atoms. These orbitals are normally filled with electrons, so in order to get a conduction band some oxidation (removal of electrons) must take place. This may be readily accomplished by adding a little elemental chlorine or bromine to the pure tetracyanoplatinate salt to get stoichiometries such as K-.[Pt(CN)jBr0, in which the platinum has an average oxidation state of +2.3. The oxidation may also be accomplished electrolytically. as in the preparation of Rbj(Pt(CN)4J(FHF)04 (Fig. 16.8). which has a short Pt—Pi separation. The Pt—Pt distance is only 280 pm. almost as short as that (bund in platinum metal itself (277 pm) and in oxidized platinum "pop complexes (270 to 278 pm see Chapter l5).4- Cold-bronze materials of this type were discovered as early as 1842. though they have been little understood until recent times. The complexes behave not only as one-dimensional conductors, but... 

As with alkenes, alkynes coordinate to platinum in both the zerovalent and divalen oxidation states. Since the chemistry of platinum alkyne complexes is less extensive than that c alkene complexes, this section is not subdivided into complexes of the two types. The divalen compounds of platinum will be covered first, followed by the complexes of platinum in a forms zerovalent oxidation state. 

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