ABSTRACT
Diphosphorus ligands connected by a single atom (R2PEPR2; E = CR2, C[double bond, length as m-dash]CR2 and NR) give chelating ligands with very small bite-angles (natural bite-angle of 72° for dppm) as well as enable access to other properties such as bridging modes and hemilability. Their use in catalysis has been growing over the last two decades as researchers have sought to apply the properties of small bite-angle ligands to a wide number of catalytic reactions, often complementing the well-established applications of wide bite-angle ligands in catalysis. This Perspective reviews the properties of diphosphorus ligands featuring a single-atom linker and their use in several catalytic transformations of alkenes, including selective ethene oligomerisation, ethene polymerisation and co-polymerisation with CO, hydroacylation and hydrogenation, as well as their use in transfer hydrogenation and hydrogen-borrowing reactions.
ABSTRACT
The 2-phosphinophosphinine 2-PPh2-3-Me-6-SiMe3-PC5H2 (2) has been prepared and was shown to act as a κ2-chelating ligand in cis-[RuCl2(2)2] (4). Complex 4 was a competent precatalyst for the room temperature transfer hydrogenation of acetophenone (0.1 mol% 4 and 0.5 mol% KOtBu) and the conversion of methanol/ethanol mixtures to the advanced biofuel isobutanol in 50% yield and 96% selectivity.
ABSTRACT
Three dimethyltindiamides containing chelating diamide ligands were synthesised from the reaction of the dilithiated diamine and Me2SnCl2; [SnMe2(L1)] 1 (L1 = κ(2)-N(Dipp)C2H4N(Dipp)), [SnMe2(L2)] 2 (L2 = κ(2)-N(Dipp)C3H6N(Dipp)) and [SnMe2(L3)] 3 (L3 = κ(2)-N(Dipp)SiPh2N(Dipp)), Dipp = 2,6-(i)Pr2C6H3. Reaction of (L2)H2 with SnCl4 and NEt3 led to the formation of the diamidotin dichloride [SnCl2(L2)] 4 whereas reaction of (L1)H2 with SnCl4 and NEt3, or [Sn(L1)] with SnCl4, led to the exclusive formation of the amidotin trichloride [SnCl3{κ(2)-DippN(H)C2H4N(Dipp)}] 5. Reactions of [Sn(L1)] with sulfur and selenium formed [{Sn(L1)(µ-E)}2] (E = S 10 and Se )11. MeI reacted with N-heterocyclic stannylenes to generate the Sn(iv) addition products [Sn(Me)I(L1)] 12, [Sn(Me)I(L2)] 13, [Sn(Me)I(L3)] 14 and [Sn(Me)I(L4)] 15 (L4 = κ(3)-N(Dipp)C2H4OC2H4N(Dipp)), and subsequent reaction with AgOTf (OTf = OSO2CF3) generated the corresponding Sn(iv) triflates [Sn(Me)OTf(L1)] 16, [Sn(Me)OTf(L2)] 17 and [Sn(Me)OTf(L4)] 19 with [Sn(Me)OTf(L3)] 18 formed only as a mixture with unidentified by-products. All of the compounds were characterised by single crystal X-ray diffraction.
ABSTRACT
The synthesis and X-ray crystal structures of the diborane(4) isomers 1,1-B(2){1,2-(NH)(2)C(6)H(4)}(2) and 1,2-B(2){1,2-(NH)(2)C(6)H(4)}(2) are described together with the results of quantum chemical calculations which shed light on their relative stabilities and degree of aromaticity. Spectroscopic data are also provided for both isomers of the 4-methyl aryl derivative. The compound 1,1-B(2){1-O-2-(NH)C(6)H(4)}(2) has also been prepared and structurally characterised but no evidence was obtained for the corresponding 1,2-isomer. The compound 1,1-B(2){1,2-(NH)(2)C(6)H(4)}(2) forms a co-crystal with TCNQ, the structure of which is also reported.
