Attachment of racemic 1,3,5,7-tetramethyl-2,4,6-trioxa-8-phosphatricyclo[3.3.1.13,7]decane (α,β-CgP) to (1R,5S)-1,8,8-trimethyl-2,4-diazabicyclo[3.2.1]oct-2-ene gave a diastereomeric mixture of a novel amidine–phosphine ligand, α,β-CgPAm. The phosphination was completely selective for the 4-position of the bicyclic amidine and there was no subsequent 1,2-migration of the α,β-CgP group. Methylation of the non-phosphinated nitrogen gave the amidinium salt [α,β-CgPAmMe]BF4 as a diastereomeric mixture. The donating ability of α,β-CgPAm and [α,β-CgPAmMe]+ has been assessed through the synthesis and characterization of appropriate Rh(I), Au(I) and Pt(II) complexes. As expected α,β-CgPAm is a better net donor than the cationic derivative as shown by the magnitude of the νCO stretches in the IR spectra of the [Rh(L)(CO)(acac)]0/+ complexes and through determination of the relative energies of the HOMO and LUMO orbitals for both ligands by DFT. Attempts to resolve [Au(α,β-CgPAmMe)Cl]BF4, [Pt(α,β-CgPAmMe)Cl3], [Rh(α,β-CgPAmMe)(acac)(CO)]BF4 and [Rh(α,β-CgPAmH)(acac)(CO)]BF4 by fractional crystallization were unsuccessful as diastereomeric mixtures were obtained in every case; the structures of the last three complexes have been determined by single-crystal X-ray techniques and compared with related literature complexes.

An asymmetric heterotopic ligand (S-NMeCP) containing a central bicyclic, expanded-ring NHC with one pyridyl and one phosphine exo-substituent has been synthesised and its coordination chemistry with selected late transition metals investigated. The amidinium precursor [S-NMeCHP]PF6 shows variable coordination modes with Ag(I), Cu(I) and Au(I) depending on the L:M ratio. The reaction of two mols of [S-NMeCHP]PF6 with [Cu(MeCN)4]BF4, AgBF4 or Au(THT)Cl gives the bis-ligand complexes [Cu(κ-P-NMeCHP)2(CH3CN)2]BF4·(PF6)2, 1, and [M(κ-P-NMeCHP)2]X·(PF6)2 (3: M = Ag, X = BF4; 6: M = Au, X = Cl) respectively. The 1:1 reaction of [S-NMeCHP]PF6 with AgOTf gave the head-to-tail dimer H,T-[Ag2(μ-N,P-NMeCHP)2(μ-OTf)2](PF6)2, 2, whereas the analogous reaction with Au(THT)Cl gave monomeric [Au(κ-P-NMeCHP)Cl]PF6, 5. Complex 2 was converted to H,T-[Ag2(μ-C,P-NMeCP)2](PF6)2, 4, upon addition of base, while 6 gave [Au(κ-C-NMeCP)2]Cl, 8, when treated likewise. Reaction of [S-NMeCHP]PF6 with Ni(1,5-COD)2 gave the oxidative addition/insertion product [Ni(κ3-N,C,P-NMeCP)(η3-C8H13)]PF6, 9, which converted to [Ni(κ3-N,C,P-NMeCP)Cl]PF6, 10, upon exposure of a CHCl3 solution to air. Complex 10 showed conformational isomerism that was also present in [Rh(κ3-N,C,P-NMeCP)(CO)]PF6, 14, prepared from the precursor complex [Rh(κ-P-NMeCHP)(acac)(CO)]PF6, 13, upon heating in C6H5Cl. [Pt(κ3-N,C,P-NMeCP)(Cl)]PF6, 12, derived from trans-[Pt(κ-P-NMeCHP)2(Cl)2](PF6)2, 11, was isolated as a single conformer.

The cyclo-condensation of 1R,2R-diaminocyclohexane with 2,2′-(ethane-1,2-diyldisulfanediyl)dibenzaldehyde gave the 1:1 addition compound chxn-imN2S2 in high yield. When the same condensation reaction was performed with 1R,3S-diamino-1,7,7-trimethylcyclopentane as the diamine, the 2:2 addition compound tmcp-imN4S4 was obtained selectively. Reduction of the diimines gave the saturated analogues chxn-N2S2 (1) and tmcp-N4S4 (3) the former of which could be phosphorylated with PhP(NMe2)2 to give the novel 13-membered macrocycle chxn-PS2, 2. Introduction of the phenylphosphine function proved stereoselective with a preference for the N(R)/N(S) configuration at the nitrogen atoms. The coordination chemistry of the novel phosphine has been explored with Cu(I) and Mo(0) through formation of the complexes Cu(2)I, 4, and Mo(CO)3(2), 5. Extension of the phosphorylation chemistry to tmcp-N4S4 (3) proved unsuccessful but ring closure reactions of both 1 and 3 with triethylorthoformate gave cyclic amidinium salts which are potential precursors to macrocyclic N-heterocyclic carbenes.

A chiral, tridentate, pyridyl-functionalised NHC pro-ligand, S-LMe-H[PF6], has been prepared diastereoselectively via a five step synthesis starting from 1R,3S-diamino-1,2,2-trimethylcyclopentane. The S prefix refers to the stereochemistry of a methyl substituted stereogenic carbon in one of the pyridyl arms which is generated by a stereoselective BH4− reduction of an imine precursor. The ligand has been coordinated to Rh(I) and Ir(I) to give trigonal bipyramidal complexes of the type [M(κ3-N,C,N′-S-LMe)(1,5-COD)]PF6 (M = Rh, Ir) as single diastereomers. A combination of spectroscopic and X-ray techniques confirm the stereoselective formation of the thermodynamically preferred endo,endo isomer. Similar reactions with R,S-LMe-H[PF6] gave a mixture of endo,endo-[M(κ3-N,C,N′-S-LMe)(1,5-COD)]+ and exo,exo-[M(κ3-N,C,N′-R-LMe)(1,5-COD)]+. The absolute configuration at the metal is, therefore, solely dictated by the stereochemistry of the single methylpyridyl carbon. The observation of stereoselection extends to the square planar Ni(II) complex [Ni(δ-κ3-N,C,N′-S-LMe)Cl]+ which is isolated as one (δ) of the two possible conformational isomers. DFT studies have been employed to explain the observed stereoselectivity with the configurations observed in the solid state being confirmed as those of lowest energy.

The cationic complex (η4-1,2,3,4-tetramethylcyclobutadienyl)cobalt(trisacetonitrile), [(η4-C4Me4)Co(NCCH3)3]+ (1), allows the stepwise introduction of suitable phosphine precursors to the [(η4-C4Me4)Co]+ fragment by replacement of the labile acetonitrile ligands. These reactions give rise to the piano-stool complexes [(η4-C4Me4)Co(dppe)(NCCH3)]+ (2), [(η4-C4Me4)Co(dppe)(PH2Ph)]+ (3), [(η4-C4Me4)Co(dfppb)(NCCH3)]+ (4), and [(η4-C4Me4)Co(dfppb)(PH2Ph)]+ (5), where dfppb = 1,2-bis{di(2-fluorophenyl)phosphino}benzene and dppe = 1,2-bis(diphenylphosphino)ethane. Complex 5 is a template for the synthesis of the P3 macrocycle complex [(η4-C4Me4)Co{1,4-bis(2-fluorophenyl)-7-phenyl[b,e,h]tribenzo-1,4,7-triphosphacyclononane}]+ (6), through base-promoted intramolecular macrocyclization. The hydrogens of two of the ring methyls of the tetramethylcyclobutadienyl ligand in the macrocycle complex 6 are sufficiently acidic to undergo deprotonation by KOtBu, promoting nucleophilic attack at the fluorine-bearing ortho-carbons of the 2-fluoroaryl groups on two of the phosphorus donors in 6. The resultant hemi-incarcerand complex [{η4,κP,κP,κP-Me2C4-[1,4-bis(2-CH2C6H4)-7-C6H5-[b,e,h]tribenzo-1,4,7-triphosphacyclononane]-1,2}Co]+ (cis-7) contains a hybrid phosphorus/carbon donor ligand where the P3 macrocycle is connected to the cyclobutadienyl function through two cis-2-methylphenyl links. The new complexes have been characterized fully by spectroscopic and analytical techniques including single-crystal X-ray structure determinations of 2, 3, 4, 5, 6, and cis-7.

The reaction of 1,2-o-xylyl dichloride with activated zinc in THF gives the organozinc compound [(μ-o-xyl)Zn2Cl2(THF)4], 1, where xyl = (2-methanidylphenyl)methanide. The compound is stable in the solid state but undergoes a slow decomposition in solution to generate the μ4-oxo cluster [(μ-o-xyl)2Zn4(μ-Cl)2(μ4-O)(THF)4], 3, which has been characterised in the solid state by single-crystal X-ray techniques. The organozinc complex 1 catalyses the ring-opening of THF in the presence of PCl3 to give a mixture of the two compounds [Cl(CH2)4O]PCl2 and [Cl(CH2)4O]2PCl.An ortho-xylidenedizinc compound catalyses the room temperature ring-opening of THF by PCl3 to give 4-chlorobutyl phosphorodichloridoite and bis(4-chlorobutyl)phosphorochloridoite. The reaction occurs within minutes at room temperature using 20% of the organozinc compound.Highlights► A new o-xylidenedizinc complex has been synthesised. ► The complex abstracts oxygen from THF on standing to give a μ4-oxo tetrazinc cluster. ► The organozinc compound catalyses the ring-opening of THF with PCl3.

An unusual example of diastereoselectivity has been observed in Cu(κ3-P,C,P′-1)X complexes where 1 is an asymmetric tridentate ligand containing a bicyclic NHC framework and X is a halide. When X is Cl−, the SCu isomer is formed selectively whereas when X = I− the RCu diastereomer is preferred.

A diphosphine ligand (1·HPF66666), which is a potential precursor to a PCNHCP pincer, with a backbone containing two phenylene groups and a central bicyclic 4-aza-2-azoniabicyclo[3.2.1]oct-2-ene unit has been synthesised and coordinated to Pd(II) and Pt(II) to give trans-[M(κ2-P,P′-1·H)Cl2]PF6 where M = Pd (2) or Pt (3a). Single-crystal structure determinations of 2 and 3a show the complexes to be isostructural with the diphosphine coordinated in a trans-spanning fashion and the amidinium unit being protonated and non-coordinated. 2 and 3a react with CH3I to give the dimers trans-[Pd2(μ-1·H)2I4](PF6)2, 6, and trans-[Pt2(μ-1·H)2I4](PF6)2, 7, as the major products. This bridging mode of coordination of [1·H]+ is also seen in trans-[Rh2(μ-1·H)(1,5-COD)2Cl2]PF6, 4, and [Pt2(μ-κ2-1·H)(dvdms)]PF6, 5. Upon treatment with KOtBu complexes 2 and 3a undergo deprotonation at the amidinium carbon to give trans-[M(κ3-P,C,P′-1)Cl]PF6 where M = Pd (8), and Pt (9). The related trans-[Rh(κ3-P,C,P′-1)(CO)]PF6 (10) is prepared directly from 1·HPF66666 and Rh(acac)(CO)2: this and the palladium and platinum complexes 8 and 9 are isolated as isomeric mixtures as a consequence of a conformational isomerism. In situ deprotonation of 1·HPF66666 followed by addition of Ag(CF3SO3) gave SAg-[Ag(κ3-P,C,P′-1)(CF3SO3)], 11. Some preliminary studies of the reactivity of 2 and 8 in Suzuki-type reactions are reported and the Pt(0) system has been shown to be an active hydrosilylation catalyst.

A tridentate N⁁C⁁N ligand, 1, containing a bicyclic central NHC ring and two flanking pyridyl groups has been coordinated to Rh(I) and Ir(I) to give complexes of the type [M(κ3-1)(1,5-COD)]PF6 (2 M = Rh; 3 M = Ir). In contrast to our earlier study with this ligand, the complexes have been shown to approximate to a trigonal bipyramidal geometry in the solid state and exist as an isomeric mixture in solution as determined by 1H and 13C NMR spectroscopy. Electrochemical studies revealed that both complexes undergo a 1-electron oxidation with the potential of the Rh complex 0.1V less than that of the Ir complex in CH2Cl2. Preliminary DFT studies confirm the lowest energy conformations as those seen in the solid state and show the location and energy of the HOMOs to be identical in 2 and 3. Partial charge analysis shows a greater positive charge on the Ir in 3 compared to the Rh in 2. Some preliminary studies of hydrogenation reactivity have shown the complexes to be efficient for both transfer and direct hydrogenation of prochiral ketones and alkenes at moderate temperatures but without any discernible enantioselectivity.

The novel primary phosphine (1R,3S)-[1,2,2-trimethyl-3-(phosphinomethyl)cyclopentyl]methyl methanesulfonate 3a (or tosylate 3b) has been prepared in three steps from (1R,3S)-camphoric acid with a view to utilising it as a synthon for the preparation of polycyclic phosphines. Efforts to prepare a [3.2.1] bicyclic product by internal cyclisation of 3a or 3b under various conditions were unsuccessful, but heating the neat compound at 140 °C for several hours gave the new asymmetric, bicyclic secondary phosphine, (1R,4S,6R)-5,5,6-trimethyl-2-phosphabicyclo[2.2.2]octane (PBO) as its methanesulfonic acid 5a (or p-toluenesulfonic acid 5b) salt. The cyclisation involves a skeletal rearrangement and occurs with high stereoselectivity to generate two new stereogenic carbon centres and a chiral phosphorus atom. The secondary phosphine was obtained after base treatment of 5a/b and several derivatives of the phosphine have been synthesised and characterised. Reaction of two mol equivalents of the borane adduct of PBO with α,α′-dichloro-ortho-xylene gave the bidentate derivative, o-C6H4(CH2PBO)2.2BH3, 12, and ultimately o-C6H4(CH2PBO)2, 13. Complexes of 13 with Pd(II), Pt(II), Pt(0) and Mo(0) have been prepared and characterised by spectroscopic and analytical methods including single-crystal X-ray structure determinations of cis-Pd{o-C6H4(CH2PBO)2}Cl2, 14, cis-Pt{o-C6H4(CH2PBO)2}Cl2, 15 and Mo(CO)4{o-C6H4(CH2PBO)2} 17.

Azolium precursors to expanded-ring NHCs incorporating a chiral bicyclic skeleton derived from (1R)-camphor with N,N′-dibenzyl or N,N′-dipyridyl substituents have been prepared and used for the synthesis of a number of metal complexes of the resultant NHCs. The bicyclic framework contains two fused rings, one of which is seven-membered while the other is six-membered. Deprotonation of (1R,5S)-2,4-dibenzyl-1,8,8-trimethyl-4-aza-2-azoniabicyclo[3.2.1]oct-2-ene hexafluorophosphate, 1a·HPF6, produces a solution of “free carbene”, 1a, that can be used for the preparation of [Ag(1a)2]OTf (2a), [Rh(1,5-COD)(1a)Cl] (3a), [Rh(CO)2(1a)Cl] (4a), and [Ir(1,5-COD)(1a)Cl] (5a) complexes. The fused expanded ring NHC ligands display properties and reactivity patterns more akin to those of five-membered NHCs rather than monocyclic six- or seven-membered NHCs. Consistent with this premise, the red Ni(II) pincer complex [Ni(η3-C8H13)(1b)]PF6, 6b, was obtained via oxidative addition of the azolium salt 1b·HPF6 to Ni(1,5-COD)2 in THF. This is the first unambiguous example of a saturated and/or expanded ring NHC oxidatively adding to a low-valent metal center. A single-crystal X-ray structure determination of 6b showed the NHC to be coordinated in a pincer fashion through the carbene and two pyridine nitrogens at a square-pyramidal nickel(II) center. One of the original 1,5-COD ligands has undergone a 1,5 to 1,3 isomerization before migratory insertion of one of the alkene groups into the Ni−H function, generated on oxidative addition of the azolium salt, to give the allylic η3-C8H13 ligand. When 6b was dissolved in CHCl3 or CH2Cl2 in air, the allyl ligand was lost and a chloride was abstracted from the solvent to give yellow square-planar [Ni(1b)Cl]PF6, 7b, the structure of which was confirmed by single-crystal X-ray techniques.

Palladium(II) and platinum(II) complexes of a chiral pentacyclic phosphine, (1S, 4R, 4aS, 5aR, 6R, 9S, 9aS, 10aR)-4,6,11,11,12,12-hexamethyl-10-phenyl-dodecahydro-1,4:6,9-dimethano-phenoxaphosphinine (phenop), show diverse structures dependent upon the chosen metal-containing starting material and reaction conditions. With palladium acetate, a P,C-cyclometallated dimeric complex [Pd(μ-κ2-OAc)(μ-κ1-OAc)(κP,κC14-phenop)]2, 4, is obtained through metallation at the C(14) methyl to form a six-membered chelate. The acetato bridged dimer is readily converted to the halo-bridged species [Pd(μ-X)(κP,κC14-phenop)]2, where X is chloride (5) or bromide (6). Reaction of one equivalent of phenop with Pd(COD)Cl2 or Na2PdCl4 gives a different phosphapalladacycle dimer [Pd(μ-Cl)(κP,κC8-phenop)]2, 7, with a five-membered chelate and metallation at the C(8) methylene carbon. The analogous platinum derivative [Pt(μ-Cl)(κP,κC8-phenop)]2, 8, is obtained from the 1 ∶ 1 reaction of phenop and K2PtCl4. An unusual ligand–ligand coupled product, 9, has been isolated in low yield from the reaction of phenop and Pd(COD)Cl2. The zerovalent Pd(κP-phenop)2, 10, and a monodentate silver(I) derivative, [Ag(κP-phenop)(CF3SO3)], 11, have also been prepared. These new complexes have been fully characterised by spectroscopic and other techniques including single crystal X-ray structure determinations of phenop, 7–9 and 11.

A new sterically encumbered monophosphine has been prepared stereoselectively from (1R)-camphor and some aspects of its coordination chemistry with palladium examined.

The novel primary phosphine (1R,3S)-[1,2,2-trimethyl-3-(phosphinomethyl)cyclopentyl]methyl methanesulfonate 3a (or tosylate 3b) has been prepared in three steps from (1R,3S)-camphoric acid with a view to utilising it as a synthon for the preparation of polycyclic phosphines. Efforts to prepare a [3.2.1] bicyclic product by internal cyclisation of 3a or 3b under various conditions were unsuccessful, but heating the neat compound at 140 °C for several hours gave the new asymmetric, bicyclic secondary phosphine, (1R,4S,6R)-5,5,6-trimethyl-2-phosphabicyclo[2.2.2]octane (PBO) as its methanesulfonic acid 5a (or p-toluenesulfonic acid 5b) salt. The cyclisation involves a skeletal rearrangement and occurs with high stereoselectivity to generate two new stereogenic carbon centres and a chiral phosphorus atom. The secondary phosphine was obtained after base treatment of 5a/b and several derivatives of the phosphine have been synthesised and characterised. Reaction of two mol equivalents of the borane adduct of PBO with α,α′-dichloro-ortho-xylene gave the bidentate derivative, o-C6H4(CH2PBO)2.2BH3, 12, and ultimately o-C6H4(CH2PBO)2, 13. Complexes of 13 with Pd(II), Pt(II), Pt(0) and Mo(0) have been prepared and characterised by spectroscopic and analytical methods including single-crystal X-ray structure determinations of cis-Pd{o-C6H4(CH2PBO)2}Cl2, 14, cis-Pt{o-C6H4(CH2PBO)2}Cl2, 15 and Mo(CO)4{o-C6H4(CH2PBO)2} 17.

A diphosphine ligand (1·HPF66666), which is a potential precursor to a PCNHCP pincer, with a backbone containing two phenylene groups and a central bicyclic 4-aza-2-azoniabicyclo[3.2.1]oct-2-ene unit has been synthesised and coordinated to Pd(II) and Pt(II) to give trans-[M(κ2-P,P′-1·H)Cl2]PF6 where M = Pd (2) or Pt (3a). Single-crystal structure determinations of 2 and 3a show the complexes to be isostructural with the diphosphine coordinated in a trans-spanning fashion and the amidinium unit being protonated and non-coordinated. 2 and 3a react with CH3I to give the dimers trans-[Pd2(μ-1·H)2I4](PF6)2, 6, and trans-[Pt2(μ-1·H)2I4](PF6)2, 7, as the major products. This bridging mode of coordination of [1·H]+ is also seen in trans-[Rh2(μ-1·H)(1,5-COD)2Cl2]PF6, 4, and [Pt2(μ-κ2-1·H)(dvdms)]PF6, 5. Upon treatment with KOtBu complexes 2 and 3a undergo deprotonation at the amidinium carbon to give trans-[M(κ3-P,C,P′-1)Cl]PF6 where M = Pd (8), and Pt (9). The related trans-[Rh(κ3-P,C,P′-1)(CO)]PF6 (10) is prepared directly from 1·HPF66666 and Rh(acac)(CO)2: this and the palladium and platinum complexes 8 and 9 are isolated as isomeric mixtures as a consequence of a conformational isomerism. In situ deprotonation of 1·HPF66666 followed by addition of Ag(CF3SO3) gave SAg-[Ag(κ3-P,C,P′-1)(CF3SO3)], 11. Some preliminary studies of the reactivity of 2 and 8 in Suzuki-type reactions are reported and the Pt(0) system has been shown to be an active hydrosilylation catalyst.

An asymmetric heterotopic ligand (S-NMeCP) containing a central bicyclic, expanded-ring NHC with one pyridyl and one phosphine exo-substituent has been synthesised and its coordination chemistry with selected late transition metals investigated. The amidinium precursor [S-NMeCHP]PF6 shows variable coordination modes with Ag(I), Cu(I) and Au(I) depending on the L:M ratio. The reaction of two mols of [S-NMeCHP]PF6 with [Cu(MeCN)4]BF4, AgBF4 or Au(THT)Cl gives the bis-ligand complexes [Cu(κ-P-NMeCHP)2(CH3CN)2]BF4·(PF6)2, 1, and [M(κ-P-NMeCHP)2]X·(PF6)2 (3: M = Ag, X = BF4; 6: M = Au, X = Cl) respectively. The 1:1 reaction of [S-NMeCHP]PF6 with AgOTf gave the head-to-tail dimer H,T-[Ag2(μ-N,P-NMeCHP)2(μ-OTf)2](PF6)2, 2, whereas the analogous reaction with Au(THT)Cl gave monomeric [Au(κ-P-NMeCHP)Cl]PF6, 5. Complex 2 was converted to H,T-[Ag2(μ-C,P-NMeCP)2](PF6)2, 4, upon addition of base, while 6 gave [Au(κ-C-NMeCP)2]Cl, 8, when treated likewise. Reaction of [S-NMeCHP]PF6 with Ni(1,5-COD)2 gave the oxidative addition/insertion product [Ni(κ3-N,C,P-NMeCP)(η3-C8H13)]PF6, 9, which converted to [Ni(κ3-N,C,P-NMeCP)Cl]PF6, 10, upon exposure of a CHCl3 solution to air. Complex 10 showed conformational isomerism that was also present in [Rh(κ3-N,C,P-NMeCP)(CO)]PF6, 14, prepared from the precursor complex [Rh(κ-P-NMeCHP)(acac)(CO)]PF6, 13, upon heating in C6H5Cl. [Pt(κ3-N,C,P-NMeCP)(Cl)]PF6, 12, derived from trans-[Pt(κ-P-NMeCHP)2(Cl)2](PF6)2, 11, was isolated as a single conformer.

A tridentate N⁁C⁁N ligand, 1, containing a bicyclic central NHC ring and two flanking pyridyl groups has been coordinated to Rh(I) and Ir(I) to give complexes of the type [M(κ3-1)(1,5-COD)]PF6 (2 M = Rh; 3 M = Ir). In contrast to our earlier study with this ligand, the complexes have been shown to approximate to a trigonal bipyramidal geometry in the solid state and exist as an isomeric mixture in solution as determined by 1H and 13C NMR spectroscopy. Electrochemical studies revealed that both complexes undergo a 1-electron oxidation with the potential of the Rh complex 0.1V less than that of the Ir complex in CH2Cl2. Preliminary DFT studies confirm the lowest energy conformations as those seen in the solid state and show the location and energy of the HOMOs to be identical in 2 and 3. Partial charge analysis shows a greater positive charge on the Ir in 3 compared to the Rh in 2. Some preliminary studies of hydrogenation reactivity have shown the complexes to be efficient for both transfer and direct hydrogenation of prochiral ketones and alkenes at moderate temperatures but without any discernible enantioselectivity.

A chiral, tridentate, pyridyl-functionalised NHC pro-ligand, S-LMe-H[PF6], has been prepared diastereoselectively via a five step synthesis starting from 1R,3S-diamino-1,2,2-trimethylcyclopentane. The S prefix refers to the stereochemistry of a methyl substituted stereogenic carbon in one of the pyridyl arms which is generated by a stereoselective BH4− reduction of an imine precursor. The ligand has been coordinated to Rh(I) and Ir(I) to give trigonal bipyramidal complexes of the type [M(κ3-N,C,N′-S-LMe)(1,5-COD)]PF6 (M = Rh, Ir) as single diastereomers. A combination of spectroscopic and X-ray techniques confirm the stereoselective formation of the thermodynamically preferred endo,endo isomer. Similar reactions with R,S-LMe-H[PF6] gave a mixture of endo,endo-[M(κ3-N,C,N′-S-LMe)(1,5-COD)]+ and exo,exo-[M(κ3-N,C,N′-R-LMe)(1,5-COD)]+. The absolute configuration at the metal is, therefore, solely dictated by the stereochemistry of the single methylpyridyl carbon. The observation of stereoselection extends to the square planar Ni(II) complex [Ni(δ-κ3-N,C,N′-S-LMe)Cl]+ which is isolated as one (δ) of the two possible conformational isomers. DFT studies have been employed to explain the observed stereoselectivity with the configurations observed in the solid state being confirmed as those of lowest energy.

An unusual example of diastereoselectivity has been observed in Cu(κ3-P,C,P′-1)X complexes where 1 is an asymmetric tridentate ligand containing a bicyclic NHC framework and X is a halide. When X is Cl−, the SCu isomer is formed selectively whereas when X = I− the RCu diastereomer is preferred.

The cyclo-condensation of 1R,2R-diaminocyclohexane with 2,2′-(ethane-1,2-diyldisulfanediyl)dibenzaldehyde gave the 1:1 addition compound chxn-imN2S2 in high yield. When the same condensation reaction was performed with 1R,3S-diamino-1,7,7-trimethylcyclopentane as the diamine, the 2:2 addition compound tmcp-imN4S4 was obtained selectively. Reduction of the diimines gave the saturated analogues chxn-N2S2 (1) and tmcp-N4S4 (3) the former of which could be phosphorylated with PhP(NMe2)2 to give the novel 13-membered macrocycle chxn-PS2, 2. Introduction of the phenylphosphine function proved stereoselective with a preference for the N(R)/N(S) configuration at the nitrogen atoms. The coordination chemistry of the novel phosphine has been explored with Cu(I) and Mo(0) through formation of the complexes Cu(2)I, 4, and Mo(CO)3(2), 5. Extension of the phosphorylation chemistry to tmcp-N4S4 (3) proved unsuccessful but ring closure reactions of both 1 and 3 with triethylorthoformate gave cyclic amidinium salts which are potential precursors to macrocyclic N-heterocyclic carbenes.