A new family of long-lived alkane σ-complexes of the type (L(OEt))Re(CO)(2)(alkane) [alkane = cyclopentane, cyclohexane, pentane; L(OEt) = cyclopentadienyltris(diethylphosphito)cobaltate(III)] has been observed using both IR and NMR spectroscopies and computationally interrogated with DFT methods. The oxygen-rich coordination spheres makes these complexes perhaps more relevant as models for intermediates in metal oxide mediated hydrocarbon transformations than other known alkane σ-complexes.

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The new isonitrile-μ-carbido complexes [WPt(μ-C)Br(CNR)(PPh3)(CO)2(Tp*)] (R = C6H2Me3-2,4,6, C6H3Me2-2,6; Tp* = hydrotris(dimethylpyrazolyl)borate) rearrange irreversibly in polar solvents to provide the first examples of iminoketenylidene (CCNR) complexes.

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