Syntheses and x-ray crystal structures of two new classes of macrocyclic ligands having both phosphorus and nitrogen donor atoms

Crystal structure of 1,3-di-tert-butyl-2-chloro-1,3,2-diazaphosphorinane − a saturated six-membered phosphorus nitrogen heterocycle with a partially flattened chair conformation and a long PIII—Cl bond

“…However, two of the ring carbon atoms are bonded to exoalkylene groups and are in planar coordination. A more general search allowing for alternative P III -functionalization gave eight hits including N 1 ,N 11 :N 4 ,N 8 -bis( 2 -methylphosphino)-1,4,8,11tetraazacyclotetradecane (COLZUY; Hope et al, 1984), 1,3-di-tert-butyl-2-triphenylsilyl-1,3,2-diazaphosphorinane (DODDUV;Nifant'ev et al, 1985), the 1,3-di-tert-butyl-1,3,2diazaphosphorinanyloxy)calix(4)arenes FEMLOZ and FEMLUF (Maslennikova et al, 2004) -TED;Nifant'ev et al, 1991), the phosphatris(pyrrolyl)-and -(indolyl)methanes NEQBUG (Barnard & Mason, 2001a) and YETDIK (Barnard & Mason, 2001b) and finally 3-(tert-butyl)trimethylsilylamino-2,4-di-tert-butyl-1-[2-(1,3-di-tert-butyl-1,3,2-diazaphosphoridinyl)]imino-3-thio-1,2,4,3-thiadiazaphosphetidine (YOVYEN; Wrackmeyer et al, 1994). A search for P-chloro-functionalized six-membered ring compounds with any other three ring atoms joining the Cl-P<(NR) 2 fragment and allowing for any kind of bonding in the ring gave 16 hits including eight with three carbon atoms.…”

A General Route for the Synthesis of Triazacyclononane Functionalised with Pendant Phosphane Arms − Crystal Structures of [NiL1Cl(HOEt)][ClO4] and [NiL1(NCS)2] with L1 =N-(Diphenylphosphanylpropyl)-1,4,7-triazacyclononane

“…[1] Ϫ [3] There are a few recent examples of functionalisation by soft donor arms, for example 4-mercaptobenzoyl, [4] ϪCH 2 CH 2 SH [5] and 2-mercaptobenzyl, [6] but so far 9[ane]N 3 has not been functionalised with pendant arms ending in a phosphane group. [7] When this work was started there were only two published examples of nitrogen macrocycles with pendant phosphane arms: 1,4,8,11-tetrakis[(diphenylphosphanyl)methyl]-1,4,8,11-tetraazacyclotetradecane which is prepared by a ''one-pot'' synthesis [8] which cannot be generalised, and a series of N 2 O 2 , N 2 S 2 and NO 3 macrocycles with 2-phosphanylethyl arms. [9] Although the synthetic method used to prepare the latter series of ligands should be applicable to all nitrogen macrocycles we have not found it to be suitable in practice for 9[ane]N 3 , possibly because of the high basicity of the nitrogen atoms in this ligand.…”

Crystal Structure of N,N,N′,N′-Tetrakis(methyldiphenylphosphino)-bis-(2′-phenoxy)-3,6-dioxaoctane

“…1,2 The syntheses of some macrocyclic multidentate crown-ethers and podands containing P-C-N linkages have been reported. 3,4 The title ligand was prepared from a mixture of triethylene glycol bis(2-aminophenyl ether) 5 (2.66 g, 8.00 mmol), diphenylphosphine (5.54 mL, 32.0 mmol) and formaldehyde (7.00 mL, 37% solution in water) in benzene (150 mL) at 55˚C, with argon being passed over for 6 h. After the evaporation of benzene, the residue was crystallized from dichloromethane, yield 5.85 g (65%), m.p. 125˚C.…”