Metal-templated synthesis of a macrocyclic triphosphine-molybdenum complex, fac-(CO)3Mo(PHC3H6)3

A New Kinetic Template Synthesis of Triphosphacyclodecanes

“…For the smallest triphosphorus macrocyclic ring system ( [11]aneP 3 ) known to date, Kyba et al achieved the separation and characterization of all isomers; for the syn,syn,anti ligand isomer vigorous conditions (boiling xylenes) were required for the inversion of the phosphorus center and formation of facially coordinated complexes. [3] More recently, metal template approaches by Horner and Kunz, [4] Stelzer et al, [5] Norman et al, [6] and us [7] have been studied in order to direct the cyclization step. For facially capping triphosphanes, the template allows control of the stereochemistry at the phosphorus centers; however, liberation of the macrocycle is commonly nontrivial and to date, only 12-membered triphosphamacrocycles have been obtained as the free ligands by this method, albeit stereospecifically.…”

“…Selected bond lengths [] and angles [8]: Fe-P1 2.153(2), Fe-P2 2.148(2), Fe-P3 2.210(2), P1-Cl1 2.061(2), P2-Cl2 2.084(2); P1-Fe-P2 84.51(8), P1-Fe-P3 86.77(7), P2-Fe-P3 89.00(6).…”

A New Kinetic Template Synthesis of Triphosphacyclodecanes

“…Early preparations including those of Horner et al [1] and Kyba et al [2] were by metal-free solution or high dilution methods, and were nonstereoselective giving a mixture of all possible isomers of the macrocycles. [3] More recently, metal template approaches by Horner and Kunz, [4] Stelzer et al, [5] Norman et al, [6] and us [7] have been studied in order to direct the cyclization step. [3] More recently, metal template approaches by Horner and Kunz, [4] Stelzer et al, [5] Norman et al, [6] and us [7] have been studied in order to direct the cyclization step.…”

“…An Ortep[19] representation of the cation 5.The cyclopentadienyl methyl groups have been removed for clarity. Selected bond lengths [] and angles [8]: Fe-P1 2.153(2), Fe-P2 2.148(2), Fe-P3 2.210(2), P1-Cl1 2.061(2), P2-Cl2 2.084(2); P1-Fe-P2 84.51(8), P1-Fe-P3 86.77(7), P2-Fe-P3 89.00(6).…”

“…For the smallest triphosphorus macrocyclic ring system ( [11]aneP 3 ) known to date, Kyba et al achieved the separation and characterization of all isomers; for the syn,syn,anti ligand isomer vigorous conditions (boiling xylenes) were required for the inversion of the phosphorus center and formation of facially coordinated complexes. [3] More recently, metal template approaches by Horner and Kunz, [4] Stelzer et al, [5] Norman et al, [6] and us [7] have been studied in order to direct the cyclization step. For facially capping triphosphanes, the template allows control of the stereochemistry at the phosphorus centers; however, liberation of the macrocycle is commonly nontrivial and to date, only 12-membered triphosphamacrocycles have been obtained as the free ligands by this method, albeit stereospecifically.…”