Synthesis of TiRu₂ Heterobimetallic and TiRuM (M = Rh, Ir, Pd, Pt) Heterotrimetallic Sulfido Clusters from a Hydrosulfido-Bridged Titanium−Ruthenium Complex

Abstract

Treatment of the hydrosulfido-bridged titanium-ruthenium heterobimetallic complex [Cp2Ti(mu2-SH)2RuCl(eta5-C5Me5)] (1; Cp = eta5-C5H5) with an excess of triethylamine followed by addition of [RuCl2(PPh3)3] and [[(cod)M]2(mu2-Cl)2] (M = Rh, Ir; cod = 1,5-cyclooctadiene) led to the formation of the TiRu2 and TiRuM mixed-metal sulfido clusters [(CpTi)[(eta5-C5Me5)Ru][Ru(PPh3)2](mu3-S)2(mu2-Cl)2] (3) and [(CpTi)[(eta5-C5Me5)Ru][M(cod)](mu3-S)2(mu2-Cl)] (M = Rh (4a), Ir (4b)), respectively. On the other hand, the reactions of 1 with [M(PPh3)4] (M = Pd, Pt) afforded the TiRuM trinuclear clusters [(CpTiCl)[(eta5-C5Me5)Ru][M(PPh3)2](mu3-S)(mu2-S)(mu2-H)] (M = Pd (5a), Pt (5b)) with an unprecedented M3(mu3-S)(mu2-S) core. The detailed structures of these triangular clusters 3-5 have been determined by X-ray crystallography. Crystal data: 3, triclinic, P1, a = 12.448(4) A, b = 12.773(4) A, c = 17.270(4) A, alpha = 100.16(2) degrees, beta = 99.93(2) degrees, gamma = 114.11(3) degrees, V = 2373(1) A(3), Z = 2; 4a, triclinic, P1, a = 7.714(2) A, b = 11.598(3) A, c = 14.802(4) A, alpha = 80.46(2) degrees, beta = 82.53(2) degrees, gamma = 71.47(2) degrees, V = 1234.0(6) A3, Z = 2; 4b, triclinic, P1, a = 7.729(1) A, b = 11.577(2) A, c = 14.766(3) A, alpha = 80.14(1) degrees, beta = 82.71(1) degrees, gamma = 71.55(1) degrees, V = 1231.1(4) A3, Z = 2; 5a, monoclinic, P2(1)/c, a = 11.259(4) A, b = 16.438(4) A, c = 26.092(5) A, beta = 102.23(3) degrees, V = 4719(2) A(3), Z = 4; 5b, monoclinic, P2(1)/n, a = 11.369(2) A, b = 16.207(3) A, c = 26.116(2) A, beta = 102.29(1) degrees, V = 4701(1) A3, Z = 4.

Palladium dimethylsilanedithiolato complex: a precursor for Ti–Pd and Ti–Pd2 heterometallic complexesElectronic supplementary information (ESI) available: experimental details and spectroscopic data for 1, 2 and 3. See http://www.rsc.org/suppdata/cc/b2/b201702d/

“…The Ti-Pd distance of 3.014(1) Å is long, but it is still in the range where a weak Ti-Pd dative interaction is possible. 5 The presence of a Ti-Pd bond is consistent with the puckered TiS 2 Pd quadrilateral. The magnitude of the puckered angle (18.9°) is typical of binuclear m-sulfur complexes with a metal-metal bond.…”

“…The magnitude of the puckered angle (18.9°) is typical of binuclear m-sulfur complexes with a metal-metal bond. 5,6 The Pd-S distances (av. 2.369 Å) are similar to those of 1, and the S-Pd-S angle of 2 is increased.…”

Heterobimetallic Complexes of 1,1-Diphosphineamide Ligands

“…Complexes of these ligands have shown activity in homogeneous catalysis, with applications in reactions such as hydrogenation, hydroacylation, and hydrogen borrowing reactions . Moreover, we targeted an early/late transition metal combination for the potential of synergistic and cooperative reactivity of the two centers; ,− examples of homogeneous Ti–Rh bi- or multimetallic complexes have been reported − and used in catalysis, for example, hydrosilylation, hydroacylation, and hydrogenation reactions, with an observed enhanced reactivity of the bimetallic complex compared to their monometallic precursors.…”

The Anions [Cptt2Zr(μ-S)2M(CO)2]-(M = Rh, Ir) as Versatile Precursors for the Synthesis of Sulfido-Bridged Early−Late Heterotrimetallic (ELHT) Compounds

“…13 Noteworthy, several ELHT [TiRuM] (M ) Rh, Ir, Pd, Pt) sulfido clusters have been recently synthesized from a bis(hydrosulfido)-bridge heterobimetallic precursor having a [TiRu] metal core. 14 We report herein on the synthesis of the heterodinuclear anions [Cp tt 2 Zr(µ-S) 2 M(CO) 2 ]from the trinuclear carbonyl complexes [Cp tt 2 Zr(µ 3 -S) 2 {M(CO) 2 } 2 ] (M ) Rh, Ir) and their scope and limitations as building-blocks for the preparation of ELHT compounds. A preliminary account of part of this work was previously communicated.…”

“…The ensuing heterodinuclear anion [Cp tt 2 Zr(μ-S) 2 Ir(CO) 2 ] - behaves as a metalloligand for d 8 -[RhL 2 ] + electrophillic metal fragments affording sulfur-bridge heterotrimetallic complexes of composition [ZrRhIr] with a triangular structure . Noteworthy, several ELHT [TiRuM] (M = Rh, Ir, Pd, Pt) sulfido clusters have been recently synthesized from a bis(hydrosulfido)-bridge heterobimetallic precursor having a [TiRu] metal core …”