COMPLEXES OF THE (1R)-(-CAMPHOR AZINE DIPHOSPHINES Z,Z-3,3'-(PH2PC10H15)-C-N=N-N=(C10H15PPH2)-PH-X AND Z,Z-3,3'-(PH2PC10H15)-C-X=N-N= (C10H15PPH2)-PH-X (X = EXO, N = ENDO) WITH GROUP-6 METAL-CARBONYLS - CRYSTAL-STRUCTURES OF THE LIGANDS AND 3)(E,Z-(PH2PC10H15)-C-X=N-N=(C10H15PPH2)-PH-X)]())

Treatment of (1R)-(+)-camphor azine with 2 mole equivalents of butylli thium, followed by chlorodiphenyl-phosphine, gave the azine diphosphin es Z,Z-3,3'-(Ph2PC10H15)-C-n=N-N=(C10H15PPh2)-Ph-x I and Z,Z-3,3'-(Ph2 PC10H15)-C-x=N-N=(C10H15PPh2)-Ph-x II (x = exo, n = endo); the structu res of these were determined by X-ray diffraction. On boiling an ethan ol solution of the exo,exo-diphosphine II with sodium ethoxide or a pr opan-2-ol solution containing hydrazine hydrate and acetic acid the di phosphine isomerised to the corresponding exo,endo-diphosphine I. The corresponding diphosphine dioxides III and IV were prepared by treatin g I or II with H2O2, respectively. Treatment of I with [Mo(CO)(4)(nbd) ](nbd = norbornadiene) or with [Mo(CO)(3)(cht)](cht = cydohepta-1,3,5- triene) gave Mo(CO)(3)((Ph2PC10H15)-C-n=N-N=(C10H15PPh2)-Ph-x)] 1a. Tr eatment of I with [W(CO)(4)(nbd)] gave the tricarbonyltungsten(o) comp lex [W(CO)(3)((Ph2PC10H15)-C-n=N-N=(C10H15PPh2)-Ph-x)] 1b and the anal ogous mer complex [W(CO)(3)((Ph2PC10H15)-C-n=N-N=(C10H15PPh2)-Ph-x)] 2 . Treatment of II with [W(CO)(6)] gave the mer,exo,endo tricarbonyl co mplex 2, and the fac,endo,endo complex [W(CO)(3)((Ph2PC10H15)-C-n=N-N= (C10H15PPh2)-Ph-n)] 3. Treatment of II with [M(CO)(4)(nbd)] (M = Mo, W or Cr) gave mainly a complex of type [M(CO)(3)((Ph2PC10H15)-C-x=N-N=( C10H15PPh2)-Ph-x)] (M = Mo 4a, W 4b or Cr 4c). The crystal structure o f the tricarbonyltungsten(0) complex 4b was determined by X-ray diffra ction and the chirality around tungsten shown to be C, i.e. clockwise. Treatment of 4b with 1 mole equivalent of bromine gave the tricarbony ltungsten(II) bromide salt (CO)(3)((Ph2PC10H15)-C-x=N-N=(C10H15PPh2)-P h-x)]Br 5. Infrared, proton, phosphorus-31 and some carbon-13 NMR data are given.