Synthesis and Characterization of Coinage Metal Aluminum Sulfur Species

Abstract

The synthesis of heterobimetallic cluster with the Al-S-M (M = Cu and Ag) structural unit has been realized for the first time by the reaction of aluminum-dithiol LAl(SH)2 (L = HC[C(Me)N(Ar)]2, Ar = 2,6-iPr2C6H3) with (MesCu)4 and (MesAg)4 (Mes = 2,4,6-Me3C6H2), respectively. The isolated clusters exhibit core structures of Al2Cu4S4 and Al4Ag8S8, respectively. During the formation of the [LAl(SAg)2]4, a side product of LAlS6 is formed. However, the reaction of LAl(SH)2 with excess of sulfur and (MesAg)4 resulted in the formation of LAlS4 as the only product soluble in organic solvents. Both of them represent rare examples of aluminum polysulfides. All compounds were characterized by spectroscopic methods and single crystal X-ray diffraction studies.

Isolable Boron Persulfide: Activation of Elemental Sulfur with a 2‐Chloro‐Azaborolyl Anion

“…[20] The geometry of the three-membered BS 2 ring is approximately an isosceles triangle with three internal angles of 67.86 (7), 55.86(6), and 56.29(6)8 (the sum of the anglesi n the BS 2 three-membered ring = 180.01(6)8). The structure of 4 shows aB S 6 seven-membered ring in which the SÀSb ond length (av.2 .05 ) in 4 is noticeably shorter than that in 2 but comparable to those in the known aluminum polysulfides LAl(m-S 3 ) 2 AL (av.2 .08 ), LAlS 4 (av.2 .07 ), and LAlS 6 (av.2 .01 ) (L = HC[C(Me)N(Ar)] 2 ,A r = 2,6-iPr 2 C 6 H 3 )r eported by Roesky, [5,21] and the transition-metal polysulfide [(h 5 -MeC 5 H 4 )Ru(PPh 3 )(m-S 3 )] 2 (av.2 .05). [22] The B1ÀS1 and B1ÀS2 bond lengths of 1.899(2) and 1.948(2) i n4 are slightly lengthened compared to those in 2.…”

“…2.07 Å), and LAlS 6 (av. 2.01 Å) (L=HC[C(Me)N(Ar)] 2 , Ar=2,6‐ i Pr 2 C 6 H 3 ) reported by Roesky, and the transition‐metal polysulfide [( η 5 ‐MeC 5 H 4 )Ru(PPh 3 )( μ ‐S 3 )] 2 (av. 2.05 Å) .…”

Intramolecularly Coordinated Gallium Sulfides: Suitable Single Source Precursors for GaS Thin Films

“…Roesky et al. reported the synthesis of {HC[C(Me)N(Ar)] 2 }Al(κ 2 ‐S 4 ) (Ar=2,6‐ i Pr 2 ‐C 6 H 3 ) by reaction of {HC[C(Me)N(Ar)] 2 }Al(SH) 2 with S 8 and an indium analog, [Tm t Bu]In(κ 2 ‐S 4 ) (Tm t Bu=tris(2‐mercapto‐1‐ t Bu‐imidazolyl)hydroborato), has been prepared by oxidation of the [Tm t Bu]In(I) precursor by S 8 . These complexes have five‐membered rings with average S−S bond lengths of 2.07 Å, which are comparable to those found in 3 , with S−S bond lengths ranging from 2.0313(12)–2.0783(10) Å…”

Synthesis and Characterization of Heterobimetallic Al–O–Cu Complexes toward Models for Heterogeneous Catalysts on Metal Oxide Surfaces

“…17 On one hand, it proves that organoaluminum dihydroxide LAl(OH) 2 is essentially a reactive and useful precursor for the production of soluble heterobimetallic oxides. On the other hand, compound 4 itself can be used as an interesting precursor to evoke further reactions.…”