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In Search of Fulminate Analogues: L n M≡CP=NR.

Authors :: Frogley BJ
Hill AF
Shang R
Sharma M
Willis AC
Source :: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2020 Jul 17; Vol. 26 (40), pp. 8819-8827. Date of Electronic Publication: 2020 Jun 29.
Publication Year :: 2020
Abstract: The "CPNR" ligand may be viewed as being isolobal with fulminate, CNO; however, attempts to prepare a complex of such a ligand resulted instead in a range of novel imino and aminophosphinocarbyne complexes. Sequential treatment of [Mo(≡CBr)(CO) <subscript>2</subscript> (Tp*)] (Tp*=hydrotris(dimethylpyrazolyl)borate) with nBuLi and ClP=NMes* (Mes*=C <subscript>6</subscript> H <subscript>2</subscript> tBu <subscript>3</subscript> -2,4,6) afforded mixtures of the complexes [Mo(≡CPnBuNHMes*)(CO) <subscript>2</subscript> (Tp*)] and traces of the bimetallic products [Mo <subscript>2</subscript> {μ <subscript>2</subscript> -C <subscript>2</subscript> P <subscript>2</subscript> O(NHMes) <subscript>2</subscript> }(CO) <subscript>4</subscript> (Tp*) <subscript>2</subscript> ] and [Mo <subscript>2</subscript> (μ <subscript>2</subscript> -C <subscript>2</subscript> PNHMes)(CO) <subscript>4</subscript> (Tp*) <subscript>2</subscript> ]. The reaction of [W(≡CBr)(CO) <subscript>2</subscript> (Tp*)] with nBuLi and ClP=NMes* afforded predominantly the mononuclear carbyne [W{≡CP(=NMes*)nBu <subscript>2</subscript> })(CO) <subscript>2</subscript> (Tp*)] and traces of the binuclear complex [W <subscript>2</subscript> (μ-C <subscript>2</subscript> PNHMes)(CO) <subscript>4</subscript> (Tp*) <subscript>2</subscript> ] which is also obtained when tBuLi is used. Although not isolable, the intended complexes [M(≡CPNMes*)(CO) <subscript>2</subscript> (Tp*)] could be generated in situ and spectroscopically characterized via the reactions of the stannyl carbynes [M(≡CSnnBu <subscript>3</subscript> )(CO) <subscript>2</subscript> (Tp*)] and ClP=NMes*. The preceding observations are mechanistically interpreted with reference to a computational interrogation of the model complex [Mo(≡CP=NCH <subscript>3</subscript> )(CO) <subscript>2</subscript> (Tp*)], the LUMO of which has considerable phosphorus character.<br /> (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)