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Lewis-base Adducts of Group 1B Metal(I) Compounds. Part 16. Synthesis, Structure, and Solid-state Phosphorus-31 Nuclear Magnetic Resonance Spectra of some Novel 4X4L4> (X=Halogen, L=N, P Base) 'Cubane' Clusters

DOI: 10.1039/DT9850000831

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 831 - 838 (1985)

Update date:2022-08-03

Topics:

Authors:

Dyason, Jeffrey C.Dyason, Jeffrey C.

Healy, Peter C.Healy, Peter C.

Engelhardt, Lutz M.Engelhardt, Lutz M.

Pakawatchai, ChavengPakawatchai, Chaveng

Patrick, Vincent A.Patrick, Vincent A.

et al.et al.

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Article abstract of DOI:10.1039/DT9850000831

Recrystallization of 4I4(PPh3)4> from toluene has yielded a new polymorph of that compound, (1), which has been shown by single-crystal X-ray diffraction analysis to have a tetrametallic 'cubane' structure rather than the expected 'step' structure.Crystals are monoclinic, space group p21/n, with a=19.47(1), b=26.94(1), c=13.528(5) Angstroem, β=98.98(4) deg, Z=4 tetramers; R was 0.06 for No=3681.Cu-I distances range from 2.653(3) to 2.732(3) Angstroem, with Cu...Cu 2.874(5)-3.164(4) and I...I 4.234(2)-4.496(3) Angstroem.All adducts of stoicheiometry 4X4(PPh3)4> (M=Cu or Ag; X=Cl, Br, or I) have now been synthesized and structurally characterized in a cubane configuration.Recrystallization of copper(I) chloride and bromide from triethylamine also yields tetrameric cubane 1:1 adducts , as does the reaction of copper(I) chloride with the very bulky ligand 2-pyridine, to give 4Cl4(tmspy)4> (4).These three complexes have also been crystallographically characterized, (2) and (4) being the first reported cubane type tetramers for the copper(I) chloride-nitrogen base system.Complexes (2) and (3) are isostructural with their triethylarsine and -phosphine counterparts, being cubic, space group I43m, with a=12.162(5) Angstroem in (2) and 12.368(3) Angstroem in (3); Z=2 tetramers.Cu-Cl, Br distances are 2.441(4) and 2.537(3) Angstroem respectively.For (4), the crystals are tetragonal, space group I41/a, with a=18.620(4), c=20.079(5) Angstroem, Z=4 tetramers.Although the Cu4Cl4 cubane core of the molecule has crystallographically imposed 4 symmetry, the geometry is very unsymmetrical as a consequence of the ligand bulk, with Cu-Cl 2.225(2)-2.636(2), Cu...Cu 2.960(2)-3.194(2), and Cl...Cl 3.838(3)-3.866(3) Angstroem.Residuals R for (2), (3), (4) were 0.040, 0.038, and 0.040 respectively for No=136, 136, and 1008 'observed' reflections.The solid-state 31P n.m.r. spectra of the triphenylphosphine cubane clusters show significant differences to those with a 'step' geometry; these differences are related to the crystallographic environment of the phosphorus nuclei.

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