Crystal structure and exchange cupling of a novel binuclear palladium(I) complex

ECHEVERRÍA, GUSTAVO A.; SIVES, FLAVIO; PIRO, OSCAR E.; TARULLI, SUSANA H.; QUINZANI, OSCAR V.; FERULLO, RICARDO M.; CASTELLANI, NORBERTO

Bahia Blanca

Congreso; IV Reunión de la Asociación Argentina de Cristalografía; 2008

Universidad Nacional del Sur

We have synthesized and characterized structurally by X-ray diffraction methods a new binuclear Pd(I) complex, namely bis(thiosaccharinato)bis{bis (diphenylphosphine) methane)}dipalladium(I), where the Pd(I) ions are in the unpaired spin state 4d9 (s=1/2).The complex crystallizes in the monoclinic space group C2/c with a=13.937(3), b=19.024(2), c=23.039(4) Å, b=102.25(2)º, and Z=4 molecules per unit cell. The structure was solved from 4537 X-ray reflections with I>2s(I) by Patterson and Fourier methods and refined to an agreement R-factor of 0.0631. The Pd(I) atoms are doubly bridged by two dppm molecules through the P-atoms and the square planar environment of each metal is completed with the S-atoms of a thiosaccharinate anion and a Pd-Pd single bond, forming a Pd2P4S2 framework. It is expected a Pd(I)…Pd(I) exchange interaction giving rise to a diamagnetic (S=0) ground state and a paramagnetic (S=1) excited state. Magnetic susceptibility measurements in the 10-390 K range suggest a relatively large exchange coupling, much larger than the values of about 400 K found for related lantern-like Cu(II) 3d9 binuclear complexes. This is sustained by preliminary DFT calculations of the singlettriplet energy splitting.9 (s=1/2).The complex crystallizes in the monoclinic space group C2/c with a=13.937(3), b=19.024(2), c=23.039(4) Å, b=102.25(2)º, and Z=4 molecules per unit cell. The structure was solved from 4537 X-ray reflections with I>2s(I) by Patterson and Fourier methods and refined to an agreement R-factor of 0.0631. The Pd(I) atoms are doubly bridged by two dppm molecules through the P-atoms and the square planar environment of each metal is completed with the S-atoms of a thiosaccharinate anion and a Pd-Pd single bond, forming a Pd2P4S2 framework. It is expected a Pd(I)…Pd(I) exchange interaction giving rise to a diamagnetic (S=0) ground state and a paramagnetic (S=1) excited state. Magnetic susceptibility measurements in the 10-390 K range suggest a relatively large exchange coupling, much larger than the values of about 400 K found for related lantern-like Cu(II) 3d9 binuclear complexes. This is sustained by preliminary DFT calculations of the singlettriplet energy splitting.b=102.25(2)º, and Z=4 molecules per unit cell. The structure was solved from 4537 X-ray reflections with I>2s(I) by Patterson and Fourier methods and refined to an agreement R-factor of 0.0631. The Pd(I) atoms are doubly bridged by two dppm molecules through the P-atoms and the square planar environment of each metal is completed with the S-atoms of a thiosaccharinate anion and a Pd-Pd single bond, forming a Pd2P4S2 framework. It is expected a Pd(I)…Pd(I) exchange interaction giving rise to a diamagnetic (S=0) ground state and a paramagnetic (S=1) excited state. Magnetic susceptibility measurements in the 10-390 K range suggest a relatively large exchange coupling, much larger than the values of about 400 K found for related lantern-like Cu(II) 3d9 binuclear complexes. This is sustained by preliminary DFT calculations of the singlettriplet energy splitting.s(I) by Patterson and Fourier methods and refined to an agreement R-factor of 0.0631. The Pd(I) atoms are doubly bridged by two dppm molecules through the P-atoms and the square planar environment of each metal is completed with the S-atoms of a thiosaccharinate anion and a Pd-Pd single bond, forming a Pd2P4S2 framework. It is expected a Pd(I)…Pd(I) exchange interaction giving rise to a diamagnetic (S=0) ground state and a paramagnetic (S=1) excited state. Magnetic susceptibility measurements in the 10-390 K range suggest a relatively large exchange coupling, much larger than the values of about 400 K found for related lantern-like Cu(II) 3d9 binuclear complexes. This is sustained by preliminary DFT calculations of the singlettriplet energy splitting.2P4S2 framework. It is expected a Pd(I)…Pd(I) exchange interaction giving rise to a diamagnetic (S=0) ground state and a paramagnetic (S=1) excited state. Magnetic susceptibility measurements in the 10-390 K range suggest a relatively large exchange coupling, much larger than the values of about 400 K found for related lantern-like Cu(II) 3d9 binuclear complexes. This is sustained by preliminary DFT calculations of the singlettriplet energy splitting.9 binuclear complexes. This is sustained by preliminary DFT calculations of the singlettriplet energy splitting.