Alkynylbis(alkylidynyl)phosphines: {LnMC}2PCCR. Issue 87 (17th October 2018)

• Record Type: Journal Article
• Authors: Frogley, Benjamin J.; Hill, Anthony F.
• Is Part Of: Chemical communications. Volume 54:Issue 87(2018)
• Page Start: 12373
• Page End: 12376
• Publication Date: 2018-10-17
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/c8cc07166g
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : Synthetic strategies are presented for the formation of alkynylbis(alkylidynyl)phosphines which represent promising building blocks for unsaturated 2- and 3-dimensional assemblies. Parent ethynyl derivatives provide a means for installing further donor functionalities, e.g., AsPh2 as shown. Abstract : Sequential treatment of [M(CBr)(CO)2 (Tp*)] (M = Mo, W; Tp* = hydrotris(dimethylpyrazolyl)borate) with n BuLi, 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 n BuLi, 1/2 PCl3 and LiCCR′ affords the alkynylbis(alkylidynyl)phosphines [R′CCP{CW(CO)2 (Tp*)}2 ] (R′ = C6 H5, C6 H4 Me-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.