π-Spacer-coupled Diimidosulfinates

Schulz, Thomas; Dauer, David-Raphael

doi:10.1515/znb-2010-0607

Cited by 6 publications

(5 citation statements)

References 21 publications

(29 reference statements)

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“…Dibromobenzene (Fig.5top left), 4,4-dibromobiphenyl (Fig.5top right)34 and 9,10-dibromoanthracene35 are suitable linkers for two moieties. If 9,10-dibromoanthracene is only lithiated at one of the two positions with nBuLi and reacted with sulfur diimide the reactions proceed smoothly and afford [(thf) 2 Li(NtBu) 2 SAnBr] and [Me 2 Al(NtBu) 2 SAnBr] in a transmetalation reaction with Me 2 AlCl (An = anthracenyl, C 14 H 8 , Fig.5bottom left).…”

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confidence: 99%

Polyimido sulfur anions and ylides

Stalke

2012

Chem. Commun.

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Isovalent electronic replacement of the oxygen atoms in the classic SO(n)(m-) molecules and ions by NR imido groups yields the polyimido sulfur species S(NR)(n)(m-), n = 2, 3, 4 and m = 0, 2. The crucial cornerstone to the richness of SN chemistry is the access to sulfur diimides S(NR)(2) and triimides S(NR)(3). While the syntheses of the first are well established the preparations of the second were hazardous and of poor yields. A new facile, safe and elaborated route to give quantitative yields is presented. It involves the synthesis of triimido sulfites S(NR)(3)(2-), which are versatile ligands in their own right. With a trigonal pyramidal shape, containing three basal negatively charged nitrogen atoms, they are rare examples of dianionic tripodal ligands. Various (mixed) metal complexes are presented. Lithium coordination at the N-S-N bisections converts the dianion into the inverse tripod ligand Li(3)(NR)(3)S(+), capable of anion solvation. Among others, this motif stabilizes unprecedented monomeric methyllithium and lithium enolate. In the reaction of sulfur diimides S(NR)(2) and triimides S(NR)(3) with organometallics the diimidosulfinates RS(NR)(2)(-) and triimidosulfonates RS(NR)(3)(-) are synthesised. Both display a rich coordination chemistry to various metals, which is discussed in the review. Furthermore, the S-organo substituent can be modified in various ways. It can be a linker between two SN moieties or can be shaped to a R(2)N- or R(2)P-donating side arm of any form or length to give hemilabile scorpionates. Their ample application in metal coordination and anion solvation is presented. These monoanions can be converted to the related ylides by deprotonation of the S-alkyl group. The diimidosulfur(IV) ylides (R(2)C)S(NR)(2)(2-) and triimidosulfur(VI) ylides (R(2)C)S(NR)(3)(2-) contain the CR(2) methylene group, isoelectronic to the NR imido group. Their coordination behaviour and reactivity are discussed. In addition to the rich SN chemistry the S-N and S-C bonding is elucidated by means of theoretical and experimental charge density investigations and topological analyses on the basis of multipole refinement. As the most important result hypervalency at sulfur and S=N(C) double bonding are ruled out as superfluous concepts.

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confidence: 99%

Polyimido sulfur anions and ylides

Stalke

2012

Chem. Commun.

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“…In the reaction with Me 2 AlCl both lithium atoms are exchanged by aluminum resulting in a bimetallic symmetrical complex rather than in a heterobimetallic species. This phenomenon was already observed when benzene and biphenyl spacers were employed [20]. It seems that Me 2 AlCl is too reactive and not selective enough to exchange just one lithium atom by salt elimination.…”

Section: Synthesis Of [{(Thf) 2 Li(nr)mentioning

confidence: 85%

“…Since [(THF) 4 Li 2 {(NSiMe 3 ) 2 S} 2 biphenyl] also crystallizes as a monomer [20], it is anticipated that one reason for this uncommon structural motif is the aryl group connected to the sulfur atom. The biphenyl and the anthracene substituent both can form C-H··· π hydrogen bonds.…”

Section: Sanbr] (3) (An = Anthracenyl C 14 H 8 )mentioning

confidence: 99%

“…Unfortunately, classical transmetalation attempts with metal halides or metal amides that work with lithium organylimidosulfinates did not yield the expected products when applied to the coupled lithium imidosulfinates. Even if a reaction proceeds, not only one but both lithium atoms are exchanged leaving this route to heterobimetallic complexes closed [20]. To circumvent this problem the idea was to employ an organic spacer with two halogen atoms that can be selectively lithiated at one position first.…”

Section: Introductionmentioning

confidence: 99%

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Lithium and Aluminum Anthracenyldiimidosulfinates

Schulz¹

2010

Zeitschrift Für Naturforschung B

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9,10-Dibromo-anthracene was lithiated once or twice, and the products were reacted with different sulfurdiimides. An] (6). All products were fully characterized by X-ray structure analysis, elemental analysis, NMR and mass spectroscopy. From the solution NMR spectra it is evident that the rotation about the S-C bond is hindered even at r. t. leaving all protons of the anthracene framework non-equivalent.

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“…Moreover, Stalke et al successfully applied this particular synthetic approach also for the synthesis of Janus-type multidentate ligands as well as spacer-bridged bis(diimidosulfinates). , In addition to the well-known alkali metal and alkaline earth metal diimidosulfinates [RS(NR′) 2 ][M(solv)] [M = Li, Na, K, Rb, Cs; MgX], which are accessible either by treating sulfurdiimides with different Grignard reagents or by reaction of N , N ′-bis(trimethylsilyl)-aminoiminphenylsulphine PhS(NSiMe 3 )N(H)SiMe 3 with bis(trimethylsilyl)amides [M{(N(SiMe 3 ) 2 }] (M = Ca, Sr, Ba), , several experimental studies on the synthesis of other main group and transition metal diimidosulfinates complexes have been reported. They are almost exclusively synthesized by reaction of the alkali metal diimidosulfinates with the corresponding metal halides or amides. , Moreover, simple Lewis acid–base adducts of sulfurdiimide with several metal halides such as TiCl 4 , GaCl 3 , and SnCl 4 , respectively, have been synthesized, while Weidlein et al reported on insertion reactions of bis(trimethylsilyl)sulfurdiimide with trimethylalane, -gallane, and -indane MMe 3 (M = Al, Ga, In) . In contrast, reactions of S(NSiMe 3 ) 2 with either a zirconium imide or the titanocene alkyne complex [Cp 2 Ti(η 2 -Me 3 SiC 2 SiMe 3 )] yielded titanium trisimidosulfite complexes in a rather complex reaction mechanism, , while the analogous reaction with [Cp 2 Ti(η 2 -Me 3 SiC 2 SiMe 3 )] gave an unusual four-membered metallacycle …”

Section: Introductionmentioning

confidence: 99%

Synthesis and X-ray Crystal Structure of Diimidosulfinate Transition Metal Complexes

et al. 2015

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Bis(trimethylsilyl)sulfurdiimide S(NSiMe 3 ) 2 reacts with equimolar amounts of Me 2 Zn and Cp* 2 Zn either with insertion into the metal−carbon bond and formation of the expected S-methyl diimidosulfinate complex [MeZnN-(SiMe 3 )S(Me)NSiMe 3 ] 2 1 or the unexpected complex {Me 3 SiNS[N(SiMe 3 )-SNSiMe 3 ]N(SiMe 3 )Zn} 2 2. Insertion reactions were also observed with Cp*MMe 3 (M = Ti, Zr, Hf), yielding Cp*(Me) 2 M[Me 3 SiNS(Me)NSiMe 3 ] (M = Ti 3, Zr 4, Hf 5), whereas the corresponding Cl-substituted derivatives Cp*(Cl) 2 M[(Me 3 SiNS(Me)NSiMe 3 ] (M = Ti 6, Zr 7, Hf 8) were obtained from salt elimination reactions of Li S-methyl diimidosulfinate (Me 3 SiN) 2 S(Me)Li-(thf)] 2 9with Cp*MCl 3 . Compounds 1−8 were characterized by heteronuclear NMR ( 1 H and 13 C) and IR spectroscopy, and the solid state structures of 1−5 and 9 were determined by single crystal X-ray diffraction.

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π-Spacer-coupled Diimidosulfinates

Abstract: To synthesize ligands that are capable of coordinating two metals, 1,4-dilithiumbenzene and 4,4 -dilithiumbiphenyl were reacted with different sulfurdiimides to give coupled diimidosulfinates.[ (THF)

Cited by 6 publications

References 21 publications

Polyimido sulfur anions and ylides

Polyimido sulfur anions and ylides

Lithium and Aluminum Anthracenyldiimidosulfinates

Synthesis and X-ray Crystal Structure of Diimidosulfinate Transition Metal Complexes

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