A Tripodal Triaminostannate as a Metal Nucleophile: Synthesis of Transition Metal−Tin Heterodimetallic Complexes

Abstract

The coordination capability of the previously reported triamidostannate [MeSi{SiMe2N(4‐CH3C6H4)}3SnLi(OEt2)] (1) as a precursor for transition metal−tin heterodimetallic complexes is presented. Whereas reaction with CH3I, Me3SiCl, or Me3SnCl yielded the derivatives [MeSi{SiMe2N(4‐CH3C6H4)}3Sn−R] (R = Me, 2; Me3Si, 3; Me3Sn, 4), demonstrating the nucleophilic properties of the stannate(II), its complexation to transition metal centres was achieved by halide substitution with [CuCl(PPh3)]4, [CpM(CO)2X] (M = Fe, X = Cl; M = Ru, X = Br), [CpM(CO)3Cl] (M = Mo, W) and trans(Cl)‐[RuCl2(bpy)(CO)2] to give [MeSi{SiMe2N(4‐CH3C6H4)}3Sn−Cu(PPh3)] (5), [MeSi{SiMe2N(4‐CH3C6H4)}3Sn− M(CO)2Cp (M = Fe: 6; Ru: 7)], [MeSi{SiMe2N(4‐CH3C6H4)}3Sn−M(CO)2Cp] (M = Mo: 8; W: 9) and [(MeSi{SiMe2N(4‐CH3C6H4)}3Sn)2Ru(bpy)(CO)2] (10), of which 6, 9 and 10 were characterized by X‐ray diffraction.

119Sn NMR spectroscopic and structural properties of transition metal complexes with terminal stannylene ligands

“…The deviation may be due to the superposition of several effects (charge, steric demand, type of base). A relatively long SneW bond is also found in the triamido stannato(II) complex [{Cp(OC) 3 W}(Sn(N(p- tol)SiMe 2 ) 3 SiMe)] (9d) (2.783 A ˚) [121]. However, these two findings should not lead to the general assumption that the 17 VE fragments may lead to longer metalemetal distances.…”

119Sn NMR spectroscopic and structural properties of transition metal complexes with terminal stannylene ligands

“…The deviation may be due to the superposition of several effects (charge, steric demand, type of base). A relatively long SneW bond is also found in the triamido stannato(II) complex [{Cp(OC) 3 W}(Sn(N(p- tol)SiMe 2 ) 3 SiMe)] (9d) (2.783 A ˚) [121]. However, these two findings should not lead to the general assumption that the 17 VE fragments may lead to longer metalemetal distances.…”

Synthesis, Structures, and Reactivity of Organostannanides and Organogermanides of Copper(I)

“…The solid-state structure of 10 was not reported. [21] David Liptrot received his MChem (Hons) in Chemistry with Industrial Training from the University of Bath in 2011 and remained there to undertake a PhD on group 2 catalysis in the laboratory of Professor Mike Hill. After completing this in 2015 he took up a Lindemann Postdoctoral Fellowship with Professor Philip Power FRS (University of California, Davis, USA).…”

“…Compound 18 was reacted with 1,2-dibromoethane, generating ethene, Ph 3 GeBr, and (Ph 3 P) 3 Cu 2 Br 2 (Scheme 8). [30] In 1984, Oshima and co-workers reported a series of hydrogermylation reactions of terminal acetylenes using four lithium organogermanium cuprates, LiCu(GePh 3 ) 2 (19), LiCu(GeR 3 ) 2 (SMe 2 ) (R = Et (20), Ph (21), and Li 2 Cu(GePh 3 ) 2 (CN) (22) (Scheme 9). [31] Complexes 19-20 were synthesised in situ from the reaction of two equivalents of LiGeR 3 (R = Et, Ph) with an equivalent of CuX (X = CN, I, Br).…”

“…Identity CuÀ E bond length (Å) [a] CCDC Code [b] 1 [19] (Ph 3 P) 3 CuSnCl 3 --2 [10,25] (Me 3 P) 3 CuSnCl 3 2.5997( 14) KOTKUB 3 [10] (Me 3 P) 3 CuSnICl 2 --4 [10] (triphos)CuSnICl 3 --5 [10] (Me 3 P) 3 CuSnPh 3 --6 [10] (Ph 3 P) 3 CuSnPh 3 --7 [10] (triphos)CuSnPh 3 --8 [10] (triphos)CuSnMe 3 --9 [10] (triphos)CuSC(S)SnMe 3 -KIMNEZ 10 [21] (Ph 3 P)CuSn[{N(4-CH 3 C 6 H 4 )SiMe 2 } 3 SiMe] --11 [22] (IPr)CuSnPh 3 2.469( 5) UFOROX 12 [23] [{SnMe 2 (o-C 6 H 4 )PPh 2 } 2 CuBr] 2.6698 (7), 2.6632( 7)…”

“…In 2001, Gade, Pakkanen, and co‐workers isolated a triphenylphosphine supported copper(I) triamidostannanide, (Ph 3 P)CuSn[{N(4‐CH 3 C 6 H 4 )SiMe 2 } 3 SiMe] ( 10 ), from the salt metathesis between [Ph 3 PCuCl] 4 and Li(OEt 2 )Sn[{N(4‐CH 3 C 6 H 4 )SiMe 2 } 3 SiMe] (Scheme 2). The solid‐state structure of 10 was not reported [21] …”

119Sn NMR spectroscopic and structural properties of transition metal complexes with terminal stannylene ligands

“…The deviation may be due to the superposition of several effects (charge, steric demand, type of base). A relatively long SneW bond is also found in the triamido stannato(II) complex [{Cp(OC) 3 W}(Sn(N(p- tol)SiMe 2 ) 3 SiMe)] (9d) (2.783 A ˚) [121]. However, these two findings should not lead to the general assumption that the 17 VE fragments may lead to longer metalemetal distances.…”

Synthesis, Structures, and Reactivity of Organostannanides and Organogermanides of Copper(I)

“…The solid-state structure of 10 was not reported. [21] David Liptrot received his MChem (Hons) in Chemistry with Industrial Training from the University of Bath in 2011 and remained there to undertake a PhD on group 2 catalysis in the laboratory of Professor Mike Hill. After completing this in 2015 he took up a Lindemann Postdoctoral Fellowship with Professor Philip Power FRS (University of California, Davis, USA).…”

“…Compound 18 was reacted with 1,2-dibromoethane, generating ethene, Ph 3 GeBr, and (Ph 3 P) 3 Cu 2 Br 2 (Scheme 8). [30] In 1984, Oshima and co-workers reported a series of hydrogermylation reactions of terminal acetylenes using four lithium organogermanium cuprates, LiCu(GePh 3 ) 2 (19), LiCu(GeR 3 ) 2 (SMe 2 ) (R = Et (20), Ph (21), and Li 2 Cu(GePh 3 ) 2 (CN) (22) (Scheme 9). [31] Complexes 19-20 were synthesised in situ from the reaction of two equivalents of LiGeR 3 (R = Et, Ph) with an equivalent of CuX (X = CN, I, Br).…”

“…Identity CuÀ E bond length (Å) [a] CCDC Code [b] 1 [19] (Ph 3 P) 3 CuSnCl 3 --2 [10,25] (Me 3 P) 3 CuSnCl 3 2.5997( 14) KOTKUB 3 [10] (Me 3 P) 3 CuSnICl 2 --4 [10] (triphos)CuSnICl 3 --5 [10] (Me 3 P) 3 CuSnPh 3 --6 [10] (Ph 3 P) 3 CuSnPh 3 --7 [10] (triphos)CuSnPh 3 --8 [10] (triphos)CuSnMe 3 --9 [10] (triphos)CuSC(S)SnMe 3 -KIMNEZ 10 [21] (Ph 3 P)CuSn[{N(4-CH 3 C 6 H 4 )SiMe 2 } 3 SiMe] --11 [22] (IPr)CuSnPh 3 2.469( 5) UFOROX 12 [23] [{SnMe 2 (o-C 6 H 4 )PPh 2 } 2 CuBr] 2.6698 (7), 2.6632( 7)…”

“…In 2001, Gade, Pakkanen, and co‐workers isolated a triphenylphosphine supported copper(I) triamidostannanide, (Ph 3 P)CuSn[{N(4‐CH 3 C 6 H 4 )SiMe 2 } 3 SiMe] ( 10 ), from the salt metathesis between [Ph 3 PCuCl] 4 and Li(OEt 2 )Sn[{N(4‐CH 3 C 6 H 4 )SiMe 2 } 3 SiMe] (Scheme 2). The solid‐state structure of 10 was not reported [21] …”

119Sn NMR spectroscopic and structural properties of transition metal complexes with terminal stannylene ligands

“…The deviation may be due to the superposition of several effects (charge, steric demand, type of base). A relatively long SneW bond is also found in the triamido stannato(II) complex [{Cp(OC) 3 W}(Sn(N(p- tol)SiMe 2 ) 3 SiMe)] (9d) (2.783 A ˚) [121]. However, these two findings should not lead to the general assumption that the 17 VE fragments may lead to longer metalemetal distances.…”

Synthesis, Structures, and Reactivity of Organostannanides and Organogermanides of Copper(I)

“…The solid-state structure of 10 was not reported. [21] David Liptrot received his MChem (Hons) in Chemistry with Industrial Training from the University of Bath in 2011 and remained there to undertake a PhD on group 2 catalysis in the laboratory of Professor Mike Hill. After completing this in 2015 he took up a Lindemann Postdoctoral Fellowship with Professor Philip Power FRS (University of California, Davis, USA).…”

“…Compound 18 was reacted with 1,2-dibromoethane, generating ethene, Ph 3 GeBr, and (Ph 3 P) 3 Cu 2 Br 2 (Scheme 8). [30] In 1984, Oshima and co-workers reported a series of hydrogermylation reactions of terminal acetylenes using four lithium organogermanium cuprates, LiCu(GePh 3 ) 2 (19), LiCu(GeR 3 ) 2 (SMe 2 ) (R = Et (20), Ph (21), and Li 2 Cu(GePh 3 ) 2 (CN) (22) (Scheme 9). [31] Complexes 19-20 were synthesised in situ from the reaction of two equivalents of LiGeR 3 (R = Et, Ph) with an equivalent of CuX (X = CN, I, Br).…”

“…Identity CuÀ E bond length (Å) [a] CCDC Code [b] 1 [19] (Ph 3 P) 3 CuSnCl 3 --2 [10,25] (Me 3 P) 3 CuSnCl 3 2.5997( 14) KOTKUB 3 [10] (Me 3 P) 3 CuSnICl 2 --4 [10] (triphos)CuSnICl 3 --5 [10] (Me 3 P) 3 CuSnPh 3 --6 [10] (Ph 3 P) 3 CuSnPh 3 --7 [10] (triphos)CuSnPh 3 --8 [10] (triphos)CuSnMe 3 --9 [10] (triphos)CuSC(S)SnMe 3 -KIMNEZ 10 [21] (Ph 3 P)CuSn[{N(4-CH 3 C 6 H 4 )SiMe 2 } 3 SiMe] --11 [22] (IPr)CuSnPh 3 2.469( 5) UFOROX 12 [23] [{SnMe 2 (o-C 6 H 4 )PPh 2 } 2 CuBr] 2.6698 (7), 2.6632( 7)…”

“…In 2001, Gade, Pakkanen, and co‐workers isolated a triphenylphosphine supported copper(I) triamidostannanide, (Ph 3 P)CuSn[{N(4‐CH 3 C 6 H 4 )SiMe 2 } 3 SiMe] ( 10 ), from the salt metathesis between [Ph 3 PCuCl] 4 and Li(OEt 2 )Sn[{N(4‐CH 3 C 6 H 4 )SiMe 2 } 3 SiMe] (Scheme 2). The solid‐state structure of 10 was not reported [21] …”