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187 Os subspectra in 1 H and 31 P{ 1 H} spectra of triosmium carbonyl clusters
Author(s) -
Stchedroff Marc J.,
Aime Silvio,
Gobetto Roberto,
Salassa Luca,
Nordlander Ebbe
Publication year - 2002
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.962
Subject(s) - chemistry , diphosphines , spectral line , crystallography , phosphine , yield (engineering) , nmr spectra database , cluster (spacecraft) , stereochemistry , physics , biochemistry , astronomy , computer science , thermodynamics , programming language , catalysis
A survey of the use of 187 Os satellite subspectra in 1 H and 31 P{ 1 H} spectra of triosmium carbonyl clusters is reported. By varying evolution delays in HMQC spectra of [Os 3 (µ‐H) 2 (CO) 10 ] we have selectively extracted the values for 1 J (Os,H) and 2 J (Os,H), respectively. An analysis of the principal modes of phosphine coordination in triosmium clusters demonstrates that 31 P{ 1 H} 187 Os satellite subspectra are diagnostic for equatorial coordination [ 1 J (Os,P) = 211–223 Hz] or for axial coordination (perpendicular to the plane of the cluster) [ 1 J ( Os , P ) ≈ 147 Hz]. Chelating and bridging diphosphines yield 187 Os satellite subspectra which are the sum of A 2 X and AA′X spin systems. If significant P–P coupling is present, the AA′X component requires simulation. All observed 2 J (Os,P) trans ‐equatorial couplings fall in the range 38–65 Hz. Copyright © 2001 John Wiley & Sons, Ltd.