Phosphorus platinum-195 coupling

In review problem 8.7 we saw two examples of one-bond phosphorus-platinum coupling constant of 2380 and 4640 Hz. These are exceptionally large J values. The one-bond coupling constants most commonly encountered in NMR are iCH, iCD, yCF, yCP, and yPH. In fact, we saw examples of some of these in Section 8.6, Example 8.19, and problems 8.1, 8.4, 8.5, and 8.6. These J values are generally positive and involve nuclei with positive y values. 

A seminal paper [155] examined platinum-phosphorus NMR coupling constants in a series of cis- and trans-platinum(II and IV) complexes. The trans-influence had hitherto been explained in terms of d7r-p7r bonding, in other words, such a mechanism dominated with trans-effect... 

A related example concerns a platinum complex with phosphine and thiolate ligands that reacts via activation of a C6Fs substituent on phosphorus to couple a phosphorus ligand to a sulfur ligand forming a PtSCCP metallacycle. ... 

Poraij-Koshits MA (1978) Structural effects of mutual influence of ligands in transition- and non-transition-metal complexes. Koordinatsionnaya Khimiya 4 842-866 (in Russian) Hartley FR (1973) The cis- and trans-effects of ligands. Chem SocRev 2 163-179 Russell DR, Mazid MA, Tucker PA (1980) Crystal structures of hydrido-tris(triethyl-phosphine)platinum(II), fluoro-tris(triethylphosphine)platinum(lD, and chloro-tris(trieth-ylphosphine)platinum(II) salts. J Chem Soc Dalton Trans 1737-1742 Blau R, Espenson J (1986) Correlations of platinum-195-phosphorus-31 coupling constants with platinum-hgand and platinum-platinum bond lengths. Inotg Chem 25 878-880 Belsky VK, Konovalov 1, Kukushkin VYu (1991) Structure of cis-dichloro-(dimethyl-sulfoxide)-(pyridine)platinum(II). Acta Cryst C47 292-294... 

Phosphorus-31—tritrium couplings see Tritium—phosphorus-31 couplings Platinum chemical shift, 452 Platinum-195 NMR, 3,8,101,446,452 Platinum-195—tin-119 couplings see Tin-119—platinum-195 couplings Polarization transfer see Cross polarization and INEPT Polyamides, chemical shift, 237-38 Polyelectrolyte, 325 Poly-L-glutamic acid, 147-48 Polymers, glassy, 365 Polymorphism, 371-72... 

D. Reichenstein measured the electrode potential of phosphorus in soln. of potassium hydroxide, and sulphuric acid. R. Schenck found the potential difference of the hydrogen-phosphorus couple to be 0-168 volt at 13-6°, so that the phosphorus electrode is negative to that of hydrogen. W. Beetz studied the gas-cell with phosphorus vapour, and platinum with occluded hydrogen O. S. Duffendack and H. Huthsteiner, the low- voltage arc in phosphorus vapour. W. Busse measured the distribution of the sizes of the ions in phosphorus vapour and found that there is a continuous gradation from the largest to the smallest. 

The substantially larger values of M-p for phosphorus trans to chlorine compared with phosphorus trans to phosphorus correlate with shorter M-P bonds trans to chlorine for a number of metals and oxidation states tungsten(IV), rhodium(I) and (III), platinum(II) and (IV), and linear mercury(II) (15). By analogy with the discussion of the results for the platinum(II) complexes, this indicates the dominance of the (P sMSp)2 term in Equation 1 for couplings with a variety of M, but as discussed earlier it is difficult to determine the extent of variation of... 

Platinum-19 5—Phosphorus-31 Spin—Spin Coupling Constants in Platinum (II) Complexes... 

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