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31. Pnictogen‐Functionalised C1 Ligands: MC‐ARn (n=0, 1, 2, 3).

Author

Colebatch, Annie L., Frogley, Benjamin J., Hill, Anthony F., and Onn, Chee S.

Subjects
*LIGANDS (Chemistry), *HEAVY elements, *TRANSITION metals, *CARBYNES
Abstract

The chemistry of transition metal carbynes, LnM≡CR, has historically been dominated by species bearing hydrocarbyl or amino 'R' substituents, with other elements appearing only sporadically. In recent years, carbynes and related 'C1' species bearing other main‐group substituents, particularly heavier elements of the p‐block, have begun to emerge. This review details the chemistry of heavier pnictogen‐functionalised C1 ligands, MCARn (A=P, As, Sb, Bi; n=0–3), including their syntheses, properties and reactivities, and how these are distinguished from more traditional carbyne complexes. Recent developments in the closely related phospha‐isonitrile LnM(CPR), cya‐phosphide and cya‐arside ligands, LnM(C≡A) (A=P, As), are also discussed. [ABSTRACT FROM AUTHOR]

Published
2021
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32. In Search of Fulminate Analogues: LnM≡CP=NR.

Author

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

Subjects
*CARBYNES, *BORATES, *QUESTIONING, *PHOSPHORUS, *MIXTURES
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. [ABSTRACT FROM AUTHOR]

Published
2020
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44. Alkynylselenolatoalkylidynes (LnM≡C–Se–C≡CR) as building blocks for mixed metal/main-group extended frameworks.

Author

Frogley, Benjamin J., Genet, Tobias L., Hill, Anthony F., and Onn, Chee S.

Subjects
*PROTON transfer reactions, *LITHIUM, *THERAPEUTICS, *BORATES, *TUNGSTEN, *CHLORIDES
Abstract

The reactions of [W(≡CBr)(CO)2(Tp*)] (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with lithium alkynylselenolates LiSeC≡CR (R = SiMe3, SiiPr3, nBu, tBu, Ph, p-tolyl) afford the alkynylselenolatoalkylidyne complexes [W(≡CSeC≡CR)(CO)2(Tp*)]. Desilylation of the SiMe3 complex furnishes the parent [W(≡CSeC≡CH)(CO)2(Tp*)], which may be further derivatised by deprotonation and treatment with triphenylcarbenium or triphenylmetal chlorides to give mixed-heteroatom products [W(≡CSeC≡CEPh3)(CO)2(Tp*)] (E = C, Si, Ge, Sn, Pb). This procedure extends to dichlorosilanes, whereby the unusual bimetallic complexes [(Tp*)(CO)2W≡CSeC≡CSiRR′C≡CSeC≡W(CO)2(Tp*)] (R, R′ = Ph, CH3) are obtained, bridged by unsaturated units interrupted by two different main-group heteroatoms. Finally, the trimetallic analogues, [{(Tp*)(CO)2W(≡CSeC≡C)}3SiR] (R = Ph, Et), may be prepared in the same manner from appropriate organotrichlorosilanes. [ABSTRACT FROM AUTHOR]

Published
2019
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49. Alkynylbis(alkylidynyl)phosphines: {LnM≡C}2PC≡CR.

Author

Frogley, Benjamin J. and Hill, Anthony F.

Subjects
*CHEMICAL reactions, *PHOSPHINES
Abstract

Sequential treatment of [M(≡CBr)(CO)2(Tp*)] (M = Mo, W; Tp* = hydrotris(dimethylpyrazolyl)borate) with nBuLi, RPCl2 and LiC≡CSiMe3 affords [M{≡CPR(C≡CSiMe3)}(CO)2(Tp*)] (R = Ph, Cy) which are readily desilylated (TBAF) to provide the parent ethynyl derivatives [M{≡CPR(C≡CH)}(CO)2(Tp*)]. Alternatively, treating [W(≡CBr)(CO)2(Tp*)] with nBuLi, 1/2 PCl3 and LiC≡CR′ affords the alkynylbis(alkylidynyl)phosphines [R′C≡CP{C≡W(CO)2(Tp*)}2] (R′ = C6H5, C6H4Me-4, CMe3, SiMe3) and again the silyl derivative may be desilylated to the parent (R′ = H) which is readily converted to an arsino derivative (R′ = AsPh2). These novel architectures present new linkages for bridge-assisted polymetallic assembly. [ABSTRACT FROM AUTHOR]

Published
2018
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50. A complete set of pnictocarbynes: [M(≡CAPh2)(CO)2(Tp*)] (M = Mo, W; A = N, P, As, Sb, Bi; Tp* = hydrotris(dimethylpyrazolyl)-borate).

Author

Frogley, Benjamin J. and Hill, Anthony F.

Subjects
*CARBYNES, *METAL complexes, *PYRAZOLES
Abstract

The first two complete series of pnictogen functionalised carbyne complexes, [M(≡CAPh2)(CO)2(Tp*)] (M = Mo, W; A = N, P, As, Sb, Bi; Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate), have been prepared. The heavier analogues (A ≠ N) result from successive treatment of [M(≡CBr)(CO)2(Tp*)] with nBuLi and ClAPPh2 (A = P, Sb, Bi) or BrAsPh2 and include the first examples of arsino, stibino or bismuthino carbyne complexes. [ABSTRACT FROM AUTHOR]

Published
2018
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