In Search of Fulminate Analogues: LnM≡CP=NR

Benjamin J. Frogley; Anthony F. Hill; Rong Shang; Manab Sharma; Anthony C. Willis

doi:10.1002/chem.202000635

In Search of Fulminate Analogues: L_nM≡CP=NR

Benjamin J. Frogley, Anthony F. Hill, Rong Shang, Manab Sharma, Anthony C. Willis

Research output: Contribution to journal › Article › peer-review

11 Citations (Scopus)

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)₂(Tp*)] (Tp*=hydrotris(dimethylpyrazolyl)borate) with nBuLi and ClP=NMes* (Mes*=C₆H₂tBu₃-2,4,6) afforded mixtures of the complexes [Mo(≡CPnBuNHMes*)(CO)₂(Tp*)] and traces of the bimetallic products [Mo₂{μ₂-C₂P₂O(NHMes)₂}(CO)₄(Tp*)₂] and [Mo₂(μ₂-C₂PNHMes)(CO)₄(Tp*)₂]. The reaction of [W(≡CBr)(CO)₂(Tp*)] with nBuLi and ClP=NMes* afforded predominantly the mononuclear carbyne [W{≡CP(=NMes*)nBu₂})(CO)₂(Tp*)] and traces of the binuclear complex [W₂(μ-C₂PNHMes)(CO)₄(Tp*)₂] which is also obtained when tBuLi is used. Although not isolable, the intended complexes [M(≡CPNMes*)(CO)₂(Tp*)] could be generated in situ and spectroscopically characterized via the reactions of the stannyl carbynes [M(≡CSnnBu₃)(CO)₂(Tp*)] and ClP=NMes*. The preceding observations are mechanistically interpreted with reference to a computational interrogation of the model complex [Mo(≡CP=NCH₃)(CO)₂(Tp*)], the LUMO of which has considerable phosphorus character.

Original language	English
Pages (from-to)	8819-8827
Number of pages	9
Journal	Chemistry - A European Journal
Volume	26
Issue number	40
DOIs	https://doi.org/10.1002/chem.202000635
Publication status	Published - 17 Jul 2020
Externally published	Yes

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@article{e843c581287e4fdf81f1d0d4cd0c985d,

title = "In Search of Fulminate Analogues: LnM≡CP=NR",

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)2(Tp*)] (Tp*=hydrotris(dimethylpyrazolyl)borate) with nBuLi and ClP=NMes* (Mes*=C6H2tBu3-2,4,6) afforded mixtures of the complexes [Mo(≡CPnBuNHMes*)(CO)2(Tp*)] and traces of the bimetallic products [Mo2{μ2-C2P2O(NHMes)2}(CO)4(Tp*)2] and [Mo2(μ2-C2PNHMes)(CO)4(Tp*)2]. The reaction of [W(≡CBr)(CO)2(Tp*)] with nBuLi and ClP=NMes* afforded predominantly the mononuclear carbyne [W{≡CP(=NMes*)nBu2})(CO)2(Tp*)] and traces of the binuclear complex [W2(μ-C2PNHMes)(CO)4(Tp*)2] which is also obtained when tBuLi is used. Although not isolable, the intended complexes [M(≡CPNMes*)(CO)2(Tp*)] could be generated in situ and spectroscopically characterized via the reactions of the stannyl carbynes [M(≡CSnnBu3)(CO)2(Tp*)] and ClP=NMes*. The preceding observations are mechanistically interpreted with reference to a computational interrogation of the model complex [Mo(≡CP=NCH3)(CO)2(Tp*)], the LUMO of which has considerable phosphorus character.",

keywords = "alkylidyne, binuclear, carbyne, fulminate, iminophosphane",

author = "Frogley, {Benjamin J.} and Hill, {Anthony F.} and Rong Shang and Manab Sharma and Willis, {Anthony C.}",

note = "Funding Information: We gratefully acknowledge the Australian Research Council (DP170102695 and DP190100723) for funding. Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2020",

month = jul,

day = "17",

doi = "10.1002/chem.202000635",

language = "English",

volume = "26",

pages = "8819--8827",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-Blackwell",

number = "40",

}

TY - JOUR

T1 - In Search of Fulminate Analogues

T2 - LnM≡CP=NR

AU - Frogley, Benjamin J.

AU - Hill, Anthony F.

AU - Shang, Rong

AU - Sharma, Manab

AU - Willis, Anthony C.

PY - 2020/7/17

Y1 - 2020/7/17

N2 - 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)2(Tp*)] (Tp*=hydrotris(dimethylpyrazolyl)borate) with nBuLi and ClP=NMes* (Mes*=C6H2tBu3-2,4,6) afforded mixtures of the complexes [Mo(≡CPnBuNHMes*)(CO)2(Tp*)] and traces of the bimetallic products [Mo2{μ2-C2P2O(NHMes)2}(CO)4(Tp*)2] and [Mo2(μ2-C2PNHMes)(CO)4(Tp*)2]. The reaction of [W(≡CBr)(CO)2(Tp*)] with nBuLi and ClP=NMes* afforded predominantly the mononuclear carbyne [W{≡CP(=NMes*)nBu2})(CO)2(Tp*)] and traces of the binuclear complex [W2(μ-C2PNHMes)(CO)4(Tp*)2] which is also obtained when tBuLi is used. Although not isolable, the intended complexes [M(≡CPNMes*)(CO)2(Tp*)] could be generated in situ and spectroscopically characterized via the reactions of the stannyl carbynes [M(≡CSnnBu3)(CO)2(Tp*)] and ClP=NMes*. The preceding observations are mechanistically interpreted with reference to a computational interrogation of the model complex [Mo(≡CP=NCH3)(CO)2(Tp*)], the LUMO of which has considerable phosphorus character.

AB - 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)2(Tp*)] (Tp*=hydrotris(dimethylpyrazolyl)borate) with nBuLi and ClP=NMes* (Mes*=C6H2tBu3-2,4,6) afforded mixtures of the complexes [Mo(≡CPnBuNHMes*)(CO)2(Tp*)] and traces of the bimetallic products [Mo2{μ2-C2P2O(NHMes)2}(CO)4(Tp*)2] and [Mo2(μ2-C2PNHMes)(CO)4(Tp*)2]. The reaction of [W(≡CBr)(CO)2(Tp*)] with nBuLi and ClP=NMes* afforded predominantly the mononuclear carbyne [W{≡CP(=NMes*)nBu2})(CO)2(Tp*)] and traces of the binuclear complex [W2(μ-C2PNHMes)(CO)4(Tp*)2] which is also obtained when tBuLi is used. Although not isolable, the intended complexes [M(≡CPNMes*)(CO)2(Tp*)] could be generated in situ and spectroscopically characterized via the reactions of the stannyl carbynes [M(≡CSnnBu3)(CO)2(Tp*)] and ClP=NMes*. The preceding observations are mechanistically interpreted with reference to a computational interrogation of the model complex [Mo(≡CP=NCH3)(CO)2(Tp*)], the LUMO of which has considerable phosphorus character.

KW - alkylidyne

KW - binuclear

KW - carbyne

KW - fulminate

KW - iminophosphane

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U2 - 10.1002/chem.202000635

DO - 10.1002/chem.202000635

M3 - Article

C2 - 32372446

AN - SCOPUS:85087170871

SN - 0947-6539

VL - 26

SP - 8819

EP - 8827

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 40

ER -

In Search of Fulminate Analogues: L_nM≡CP=NR

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