Home Inorganic • Download e-book for iPad: 31P and 13C NMR of Transition Metal Phosphine Complexes by Paul S. Pregosin, Roland W. Kunz

Download e-book for iPad: 31P and 13C NMR of Transition Metal Phosphine Complexes by Paul S. Pregosin, Roland W. Kunz

By Paul S. Pregosin, Roland W. Kunz

ISBN-10: 3642488307

ISBN-13: 9783642488306

ISBN-10: 3642488323

ISBN-13: 9783642488320

For virtually 1 / 4 of a century the phrases "nuclear magnetic reso­ nance" have been synonymous with proton I,leasurements. in this interval the literature abounded with a doubtless endless number of 1H NHR experiences involved basically with carbon chemistry. sometimes a "novel" nucleus was once studied and, even in these early days, the poten- thirteen 14 31 19 tial provided by means of C, N, P and F used to be truly well-known. regardless of the attract, the technical problems desirous about measuring a few of these nuclei have been faraway from trivial. Small magnetic moments and occasional common abundance together with spin-spin coupling from different nuclei, normally protons, ended in a signal-to-noise challenge whose severity successfully excluded the research of steel complexes with unfa­ vorable solubility features. the 1st vital step forward got here with the appearance of large band 1H-decoupling. for instance, the featureless extensive 31p resonance linked to the generally used ligand triphenyl phosphine is switched over to a pointy, extra with ease ob­ served singlet while wide-band decoupling is hired (see Fig. 1). regardless of this development research of extra fascinating molecules, corresponding to catalytically energetic complexes was once compelled to wait for the devel­ opment of Fourier remodel equipment given that basically with particularly quick sign averaging tools might enough signal-to-noise ratios be achieved.

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The values of 1J (W,p) in this series span the range 143 - 485 Hz [59,104]. The extent to which metal-phosphorus d+p TI back bonding influences the mag- nitudes of the one-bond coupling in the cis and trans vi (CO) 4 (PR 3 ) 2 derivatives, structures VII and VIII, remains under discussion [77,106]. ; CO (VII) PR 3 Coupling Constants 38 In addition to the studies involving monodentate phosphines there have been a relatively large number of reports involving bidentate phosphine ligands and some involving tri- and tetradentate systems.

7%) have been tabulated are Coupling Constants 42 PBMe2Ph PMe2Ph 2+ CI"-..... ~ /C"-.. ~ /PMe2Ph Rh Rh PhMe2PA/~ ............ CI PBMe2Ph PMe2Ph PCY3 H"-..... ~ Rh /~llllll''6/ H/~ ......... H PCY3 'J(Rh, PAl = 119 Hz, 'J(Rh, PB) = 83 Hz 'J(Rh, P) = 108 Hz (XX) (XXI) 'J(Rh, P) = 133 Hz (XXII) conveniently divided into two classes: those in which the NtiR spectroscopy features prominently and those in which it is incidental. In the first category one finds that emphasis is generally placed on the relation between the chemical environment of the metal and 1J (pt,p).

97 KHz [100]. The one-bond coupling for the complexes Hg(PMe 3 )n 2 +, n = 2-4 decreases with increasing n (5505, 3580 and 2255 Hz for n = 2, 3, 4 respectively) thus clearly demonstrating the importance of the coordination number for this type of coupling [51]. A sampling of data is shown in Table 13 (Chap. G). 3% respectively). These two isotopic one-bond couplings are readily distinguishable and have been observed in the complexes CdI 2 P 2 , = PMe 2 Ph, PMePh 2 , PEt 3 , PEt 2 Ph, PEtPh 2 [101] and the dimeric species t Cd 2 X4 (PBU 3 )2' X = Cl, Br, I, SCN [102].

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31P and 13C NMR of Transition Metal Phosphine Complexes by Paul S. Pregosin, Roland W. Kunz


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