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187Os subspectra in 1H and 31P{1H} spectra of triosmium carbonyl clusters

✍ Scribed by Marc J. Stchedroff; Silvio Aime; Roberto Gobetto; Luca Salassa; Ebbe Nordlander

Publisher: John Wiley and Sons
Year: 2002
Tongue: English
Weight: 151 KB
Volume: 40
Category: Article
ISSN: 0749-1581
DOI: 10.1002/mrc.962

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✦ Synopsis

Abstract

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.

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