Synthesis and Characterization of Bimetallic Single‐Source Precursors (Ph₃P)₂M(µ‐SEt)₂E(SEt)₂ for MES₂ Chalcopyrite Materials (M = Cu, Ag and E = In, Ga, Al)

Abstract

We report the synthesis and characterization of I-III bimetallic complexes (Ph 3 P) 2 M(μ-SEt) 2 E(SEt) 2 (M = Cu, Ag and E = In, Ga, Al), as well as (Ph 3 P) 2 M(μ-Cl) 2 ECl 2 complexes isolated during their syntheses. The thiolate complexes can be used as single-source precursors (SSPs) to prepare various I-III chalcogenide semiconductor materials. The preparation of some SSPs [a]

Coinage metal aluminyl complexes: probing regiochemistry and mechanism in the insertion and reduction of carbon dioxide

“…4 Such systems also offer potential as single source precursors for metal alloys and functional materials. [5][6][7][8] Of particular interest are binuclear systems featuring elements from group 13 (Chart 1). The presence of a strongly Lewis acidic centre in close proximity to a d-block metal can assist in substrate activation, and has proven effective, for example, in mixed transition metal/aluminium systems for alkene polymerisation.…”

Molecular precursor approach to develop catalytically relevant nanosized metals, palladium chalcogenides and ternary/quaternary metal chalcogenides

“…93 This procedure has been extended to prepare [(PPh 3 ) 2 M(μ-SEt) 2 M′(SEt) 2 ] (M = Cu ( 35 ) or Ag ( 36 ); M′ = Al ( 35a , 36a ), Ga ( 35b , 36b ), In ( 35c , 36c )) using [(PPh 3 ) 2 M(μ-Cl) 2 M′Cl 2 ] and NaSEt in hot benzene. 94 The SEt group in [(PPh 3 ) 2 Cu(μ-SEt) 2 In(SEt) 2 ] ( 37 ) can be substituted by other thiolate/selenolate groups by treatment with REH and products of general formula [(PPh 3 ) 2 Cu(μ-ER) 2 In(ER) 2 ] (ER = SBu ( 38 ), SHex ( 39 ), SDodec ( 40 ), SPh ( 40 ), SePh ( 42 )) and [(PPh 3 ) 2 Cu(μ-SEt) 2 In(EPh) 2 ] (E = S ( 43 ) or Se ( 44 )) are isolated in nearly quantitative (97–99%) yields. 64 This method has been scaled up to produce [(PPh 3 ) 2 Cu(μ-SPh) 2 In(SPh) 2 ] ( 45 ) on a 500 g scale in less than one hour.…”

“…2) exhibits a core comprising of a four membered “CuIn(μ-SeR) 2 ” ring. 94 The four-membered ring, in general, adopts a planar conformation, 93–97 but it is puckered in [(PPh 3 ) 2 Ag(μ-SEt) 2 M′(SEt) 2 ] (M′ = Al ( 47 ), Ga ( 48 ), In ( 49 )) and [(PPh 3 ) 2 Cu(μ-SEt) 2 Ga(SEt) 2 ] 63 ( 50 ). The coordination environment around each metal is completed by two tertiary phosphines on copper/silver and two terminal chalcogenolates on the group-III metal ion.…”

“…The percentage weight loss in TG analysis of [(PBu 3 ) 2 Cu(μ-SEt) 2 M′(SEt) 2 ] ( 51 ), [(PBu 3 ) 2 Cu(μ-S n Pr) 2 M′(S n Pr) 2 ] ( 52 ), [(PBu 3 ) 2 Cu(μ-S i Bu) 2 M′(S i Bu) 2 ] ( 53 ), [(PBu 3 ) 2 Cu(μ-SPh) 2 M′(SPh) 2 ] ( 54 ), [(PBu 3 ) 2 Cu(μ-SeEt) 2 M′(SeEt) 2 ] ( 55 ), [(PBu 3 ) 2 Ag(μ-SEt) 2 M′(SEt) 2 ] ( 56 ), [(PBu 3 ) 2 Ag(μ-S n Pr) 2 M′(S n Pr) 2 ] ( 57 ), [(PBu 3 ) 2 Ag(μ-S i Bu) 2 M′(S i Bu) 2 ] ( 58 ), [(PBu 3 ) 2 Ag(μ-SPh) 2 M′(SPh) 2 ] ( 59 ), [(PBu 3 ) 2 Ag(μ-SeEt) 2 M′(SeEt) 2 ] ( 60 ), [(PPh 3 ) 2 Cu(μ-SEt) 2 M′(SEt) 2 ] (6 1 ), [(PPh 3 ) 2 Cu(μ-S n Pr) 2 M′(S n Pr) 2 ] ( 62 ), [(PPh 3 ) 2 Cu(μ-S i Bu) 2 M′(S i Bu) 2 ] ( 63 ), [(PPh 3 ) 2 Cu(μ-SPh) 2 M′(SPh) 2 ] ( 64 ), [(PPh 3 ) 2 Cu(μ-SeEt) 2 M′(SeEt) 2 ] ( 65 ), [(PPh 3 ) 2 Ag(μ-SEt) 2 M′(SEt) 2 ] ( 66 ), [(PPh 3 ) 2 Ag(μ-S n Pr) 2 M′(S n Pr) 2 ] ( 67 ), [(PPh 3 ) 2 Ag(μ-S i Bu) 2 M′(S i Bu) 2 ] ( 68 ), [(PPh 3 ) 2 Ag(μ-SPh) 2 M′(SPh) 2 ] ( 59 ), and [(PPh 3 ) 2 Ag(μ-SeEt) 2 M′(SeEt) 2 ] ( 69 ) (M′ = Al ( 51a–69a ), Ga ( 51b–69b ), In ( 51c–69c )) is consistent with the formation of MM′E 2 materials. 90,94,98 Nanomaterials of CuInS 2 have been prepared through decomposition of ( 51c–55c , 61c–65c ), with [(PPh 3 ) 2 Cu(μ-SEt) 2 In(SEt) 2 ] ( 61c ) being the most common precursor, by conventional thermolysis, 99–101 photolysis 102 and microwave irradiation. 92,103,104…”

“…95 Molecular structures of several of these complexes revealed tetrahedrally coordinated metal ions (Cu/Ag and Al/Ga/In) bridged by two chalcogenolate groups forming a four membered ''MM 0 (m-ER) 2 '' ring (RE = SMe, SEt, SPh, SeEt, SePh, SeBz). 90,91,[94][95][96] For example, the molecular structure of [(PPh 3 ) 2 Cu(m-SeBz) 2 In(SeBz) 2 ] (46) (Fig. 2) exhibits a core comprising of a four membered ''CuIn(m-SeR) 2 '' ring.…”