The sulphonation of [Pd(CH2CH2CH2CH2M)(tmen)] (1a) and [PdMe2(tmen)] (1b) (tmen = Me2NCH2CH2NMe2) in CH2Cl2 leads to the corresponding disulphinato compounds [Pd{S(O)2CH2CH2CH2CH 2S](O)2}(tmen)] (2a) and [Pd{S(O)2Me}2(tmen)] (2b), while the reaction of (1a) and (1b) with liquid SO2 gives the derivatives [Pd{S(O)2CH2CH2CH2CH 2S(O)2}(tmen)]·2SO2 (3a) and [Pd{S(O)2Me}2(tmen)]·2SO2 (3b) respectively. On heating under vacuum, (3a), and (3b) lose SO2 and revert to the disulphinates (2a) and (2b), respectively, which give (3a) and (3b) on reaction with liquid SO2. The X-ray crystal structures of complexes (2a) and (2b) have been determined: (2a), a = 9.259(8), b = 13.380(10), c = 6.213(5) Å, β = 92.96(2)°, space group P21, Z = 2, R = 0.0325 for 2 619 observed reflections; (2b), a = 9.377(2), c = 16.182(3) Å, space group P41212, Z = 4, R = 0.0396 for 1 249 observed reflections. The absolute configurations of the two structures have been determined, and the conformations of the two molecules compared. The metal co-ordination in both compounds is square planar with a very small tetrahedral deformation: av. Pd-S 2.288(1) and av. Pd-N 2.168(4) Å. Closure of the Pds(CH2)4S chelate ring in compound (2a) causes a small increase in the S-Pd-S angle which is 91.3(1)° in (2a) and 90.3(1)° in (2b), but does not significantly influence the co-ordination of the diamine [av. N-Pd-N 82.9(1)°]. The conformation of the palladadithiaheptane ring in (2a) is twisted-boat.

Sulphonation of Palladium-Carbon Bonds: Synthesis and X-Ray Crystal Structures of the Disulphinato Derivatives [Pd{S(O)2CH2CH2CH2CH2S(O)2}(tmen)](tmen=Me2NCH2CH2NMe2) and [Pd{S(O)2Me}2(tmen)]

DIVERSI, PIETRO;INGROSSO, GIOVANNI;LUCHERINI, ANTONIO;MARCHETTI, FABIO;MERLINO, STEFANO;
1988

Abstract

The sulphonation of [Pd(CH2CH2CH2CH2M)(tmen)] (1a) and [PdMe2(tmen)] (1b) (tmen = Me2NCH2CH2NMe2) in CH2Cl2 leads to the corresponding disulphinato compounds [Pd{S(O)2CH2CH2CH2CH 2S](O)2}(tmen)] (2a) and [Pd{S(O)2Me}2(tmen)] (2b), while the reaction of (1a) and (1b) with liquid SO2 gives the derivatives [Pd{S(O)2CH2CH2CH2CH 2S(O)2}(tmen)]·2SO2 (3a) and [Pd{S(O)2Me}2(tmen)]·2SO2 (3b) respectively. On heating under vacuum, (3a), and (3b) lose SO2 and revert to the disulphinates (2a) and (2b), respectively, which give (3a) and (3b) on reaction with liquid SO2. The X-ray crystal structures of complexes (2a) and (2b) have been determined: (2a), a = 9.259(8), b = 13.380(10), c = 6.213(5) Å, β = 92.96(2)°, space group P21, Z = 2, R = 0.0325 for 2 619 observed reflections; (2b), a = 9.377(2), c = 16.182(3) Å, space group P41212, Z = 4, R = 0.0396 for 1 249 observed reflections. The absolute configurations of the two structures have been determined, and the conformations of the two molecules compared. The metal co-ordination in both compounds is square planar with a very small tetrahedral deformation: av. Pd-S 2.288(1) and av. Pd-N 2.168(4) Å. Closure of the Pds(CH2)4S chelate ring in compound (2a) causes a small increase in the S-Pd-S angle which is 91.3(1)° in (2a) and 90.3(1)° in (2b), but does not significantly influence the co-ordination of the diamine [av. N-Pd-N 82.9(1)°]. The conformation of the palladadithiaheptane ring in (2a) is twisted-boat.
Diversi, Pietro; Ingrosso, Giovanni; Lucherini, Antonio; Lumini, T; Marchetti, Fabio; Merlino, Stefano; Adovasio, V; Nardelli, M.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11568/12352
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