A New Kinetic Template Synthesis of Triphosphacyclodecanes

Template controlled synthesis of a coordinated [11]ane-P2CNHC macrocycle

“…2 Besides A featuring amine donor groups more recently the synthesis and coordination chemistry of triphosphorus macrocycles has been investigated. Complexes containing 9-, 3 10-, 4 11-5 and 12-6 membered macrocyclic P 3 ligands are known. Gladysz and coworkers reported the synthesis of a complex with a 45-membered P 3 macrocycle by ring closing metathesis at a tungsten template.…”

“…The macrocycle [11]ane-P 2 C NHC in complex [5]Cl was synthesised by a template controlled cyclisation reaction. Initially, an easy to functionalise NH,NH-stabilised carbene ligand was generated at the rhenium(I) template (complex [1]) followed by the introduction of diphosphine 3 to give complex [4]Cl. Subsequently the coordinated diphosphine and the NH,NH-stabilised carbene ligand were connected via two new N-C bonds leading to the complex with the macrocyclic ligand.…”

“…The molecular structure of 3 § is described in the ESI. { Reaction of [1] with 3 in refluxing acetonitrile leads to the substitution of the chloro ligand as well as of one CO ligand in nearly quantitative yield (98%) and formation of [4]Cl (Scheme 2). Complex [4]Cl has been characterised by spectroscopy{ and X-ray crystallography.…”

Early Transition Metal Complexes of Triphosphorus Macrocycles

“…This might result from the flexibility of the 12-membered macrocycle as well as stereochemically nonrigid (and intrinsically more reactive) seven-coordination. Consequently, smaller ring macrocycles might be expected to form more stable systems and the study of 9-, [26,27] 10-, [28] and 11-membered triphosphorus macrocycles is in progress.…”

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“…134 The preparation and structural characterisation of the base-free osmium silylene complex [Os(NSiMe 2 )(PMe 3 ) 2 Cp*][B(C 6 F 5 ) 4 ] have been described, and it displays previously unknown reactivity towards chlorocarbons. 135 A series of four papers has been published describing the synthesis of novel new triphosphorus macrocycles, including [Fe(h 3 -1,5,9-[12]aneP 3 Et 3 )Cp][PF 6 ], 136 the first nine-membered triphosphorus macrocycle, {h 3 -meso-2,5,8-triethyl-2,5,8-triphosphabicyclo[7.4.0]trideca-9(1),10,12-triene}(pentamethylcyclopentadienyl)iron hexafluorophosphate (crystallographically characterised), 137 the first ten-membered triphosphorus macrocycle with three inequivalent phosphorus centres, 25 (crystallographically characterised), 138 and the first 1,4,7-triphosphacyclononane derivatives, [Fe(9aneP 3 -Et 3 )Cp*][BF 4 ] (also structurally characterised). 139 The complexes [Ru(h 4 -MeCHNCHCHNCHCO 2 H)Cp*]X [X = CF 3 SO 3 2 or B{C 6 H 3 (CF 3 ) 2 -3,5} 4 2 (structurally characterised)] have been shown to be very effective catalysts for hydrogenation of sorbic acid to cis-hex-3-enoic acid and of sorbic alcohol to cis-hex-3-en-1-ol under gentle conditions in two-phase liquid systems.…”