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Synthesis and X‐Ray Structures of Novel Lead(1+) and Indium(3+) Phosphazenide Complexes; Detailed 207 Pb‐NMR Spectra of the 207 Pb‐Labelled Dimeric Lead(1+) Species
Author(s) -
Winkler Astrid,
Bauer Walter,
Heinemann Frank W.,
GarciaMontalvo Veronica,
Moll Matthias,
Ellermann Jochen
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199804)1998:4<437::aid-ejic437>3.0.co;2-9
Subject(s) - chemistry , nmr spectra database , isotopomers , indium , crystallography , crystal structure , covalent bond , spectral line , stereochemistry , molecule , organic chemistry , physics , astronomy
The reaction of PbCl 2 with LiN(PPh 2 ) 2 ( 1 ) at −78°C affords the P−P coupled phosphazene Ph 2 P−N=PPh 2 −PPh 2 =N−PPh 2 ( 2 ) as an oxidation product and, as a reduction equivalent, the novel lead(1+) complex [(Pb 1+ ) 2 (μ‐Ph 2 P···N···PPh 2 − ) 2 ](Pb−Pb) ( 3 ). The crystal structure determination of the red compound 3 shows a Pb−Pb bond length of 304.1(1) pm. The 31 P‐ and 207 Pb‐NMR spectra of 3 are complicated due to the presence of a higher order spin system (AA′A′′A′′′X for the mono‐ 207 Pb isotopomer, AA′A′′A′′′XX′ for the bis‐ 207 Pb isotopomer). Simulations of the 31 P and 207 Pb spectra both on material with natural isotope abundance and on the 207 Pb‐labelled compound ( 3* ) reveal a large Pb,Pb coupling constant of 7708 Hz, indicative of a covalent Pb−Pb bond. − Though InCl 3 is diagonally related to PbCl 2 , no significant redox process is observed in the reaction between InCl 3 and 1 . The yellow crystals of [In 3+ (Ph 2 P···N···PPh 2 − ) 3 ] ( 4 ) that are obtained were also investigated by X‐ray analysis. These show a propeller‐like configuration of the three four‐membered chelate rings with indium(3+) as the centre.