Tetrathioquadratat, C
            <sub>4</sub>
            S, ein vielseitiger Ligand in Metallkomplexen, II

Grenz, Reinhard; Götzfried, Franz; Nagel, Ulrich; Beck, Wolfgang

doi:10.1002/cber.19861190412

Cited by 23 publications

(8 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[ The PPh 4 + cation in 3 shows the expected tetrahedral shape and its bond lengths and bond angles are in agreement with those previously reported in other compounds. [19][20][21][22] Each cation is involved in a parallel-fourfoldphenyl-embrace (P4PE), in which two phenyl rings are approximately parallel and the motif comprises one offset-face-to-face (off) and two edge-to-face (ef) attractive phenyl interactions. 23 The N-C and C-C distances and the N-C-C and C-C-C angles of each tetrahedral NBu 4 + cation in 4 are affected by same scatterings.…”

Section: Description Of the Structures Of (Pph 4 )[Recl 4 (Bpym)] (3)...mentioning

confidence: 99%

A novel series of rhenium-bipyrimidine complexes: synthesis, crystal structure and electrochemical properties

et al. 2007

View full text Add to dashboard Cite

Four novel rhenium complexes of formula [ReCl(4)(bpym)] (1), [ReBr(4)(bpym)] (2) PPh(4)[ReCl(4)(bpym)] (3) and NBu(4)[ReBr(4)(bpym)] (4) (bpym = 2,2'-bipyrimidine, PPh(4) = tetraphenylphosphonium cation and NBu(4) = tetrabutylammonium cation), have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. The structures of 1 and 2 consist of [ReX(4)(bpym)] molecules held together by van der Waals forces. In both complexes the Re(iv) central atom is surrounded by four halide anions and two nitrogen atoms of a bpym bidentate ligand in a distorted octahedral environment. The structures of 3 and 4 consist of [ReX(4)(bpym)](-) anions and PPh(4)(+) () or NBu(4)(+) (4) cations. The coordination sphere of the Re(iii) metal ion is the same as in 1 and 2, respectively. However, whereas the Re-X bonds are longer the Re-N bonds are shorter than in 1 and 2. This fact reveals that the bpym ligand forms a stronger bond with Re(iii) than with Re(iv) resulting in a stabilisation of the lower oxidation state. [ReX(4)(bpym)] complexes are easily reduced, chemically and electrochemically, to the corresponding [ReX(4)(bpym)](-) anions. A voltammetric study shows that the electron transference is a reversible process characterized by formal redox potentials of +0.19 V (1) and +0.32 V (2) vs. NHE, in acetonitrile as solvent.

show abstract

Section: Description Of the Structures Of (Pph 4 )[Recl 4 (Bpym)] (3)...mentioning

confidence: 99%

A novel series of rhenium-bipyrimidine complexes: synthesis, crystal structure and electrochemical properties

et al. 2007

View full text Add to dashboard Cite

show abstract

“…1 Functional materials with interesting magnetic 2 and electrooptical 3 properties in particular are frequently constructed by the assembly of mononuclear compounds and small bridging ligands to give polynuclear complexes with ligandmediated metal-metal interaction. Although a variety of sulfur donor ligands such as tetrathiooxalate 4 and tetrathio-squarate 5 have been employed for this purpose, so far, less attention has been drawn to the four-atom acetylenedithiolate ligand. The dianion (S-CtC-S) 2has the potential to support electronic communication between metal centers because each atom provides a coordination site for transition metals.…”

Section: Introductionmentioning

confidence: 99%

On the Prospects of Polynuclear Complexes with Acetylenedithiolate Bridging Units

et al. 2007

View full text Add to dashboard Cite

The generation of polynuclear complexes with one, two, or four acetylenedithiolate bridging units via the isolation of eta2-alkyne complexes of acetylenedithiolate K[Tp'M(CO)(L)(C2S2)] (Tp'=hydrotris(3,5-dimethylpyrazolyl)borate, M=W, L=CO (K-3a), M=Mo, L=CNC6H3Me2 (K-3b)) is reported. The strong electronic cooperation of Ru and W in the heterobimetallic complexes [(eta5-C5H5)(PPh3)Ru(3a)] (4a) and [(eta5-C5H5)(Me2C6H3NC)Ru(3a)] (4b) has been elucidated by correlation of the NMR, IR, UV-vis, and EPR-spectroscopic properties of the redox couples 4a/4a+ and 4b/4b+ with results from density functional calculations. Treatment of M(II) (M=Ni, Pd, Pt) with K-3a and K-3b afforded the homoleptic bis complexes [M(3a)2] (M=Ni (5a), Pd (5b), Pt (5c)), and [M(3b)2] (M=Pd (6a) and Pt (6b)), in which the metalla-acetylendithiolates exclusively serve as S,S'-chelate ligands. The vibrational and electronic spectra as well as the cyclic voltammetry behavior of all the complexes are compared. The structural analogy of 5a/5b/5c and 6a/6b with dithiolene complexes is only partly reflected in the electronic structures. The very intense visible absorptions involve essential d orbital contributions of the central metal, while the redox activity is primarily attributed to the alkyne complex moiety. Accordingly, stoichiometric reduction of 5a/5b/5c yields paramagnetic complex anions with electron-rich alkyne complex moieties being indistinguishable in the IR time scale. K-3a forms with Cu(I) the octanuclear cluster [Cu(3a)]4 (7) exhibiting a Cu4(S2C2)4W4 core. The nonchelating bridging mode of the metalla-acetylenedithiolate 3a- in 7 is recognized by a high-field shift of the alkyne carbon atoms in the 13C NMR spectrum. X-ray diffraction studies of K[Tp'(CO)(Me3CNC)Mo(eta2-C2S2)] (K-3c), 4b, 6a, 6b, and 7 are included. Comparison of the molecular structures of K-3c and 7 on the one hand with 4b and 6a/6b on the other reveals that the small bend-back angles in the latter are a direct consequence of the chelate ring formation.

show abstract

“…However, the aromaticity of thiocarbons has not been studied. The thiocarbon anions C 3 S 3 2- and C 4 S 4 2- have been synthesized, and C 4 S 4 2- , tetrathiosquarate, is a well-known and versatile ligand in metal complexes. 4b, We found no literature pertaining to C 5 S 5 2- and C 6 S 6 2- . Since Fanghänel's smooth and simple synthesis (Scheme ), C 6 S 6 6- hexaanion ( 1 ) has been used as an electroactive dendrimer core unit and as a component of a variety of electron-rich organic charge-transfer salts and transition metal complexes that sometimes exhibit redox communication between metal centers …”

Section: Introductionmentioning

confidence: 99%

A Theoretical and Structural Investigation of Thiocarbon Anions

et al. 2003

View full text Add to dashboard Cite

Density functional theory energies, geometries, and population analyses as well as nucleus-independent chemical shifts (NICS) have been used to investigate the structural and magnetic evidence for cyclic CnSn(2-) and CnSn (n = 3-6) electron delocalization. Localized molecular orbital contributions to NICS, computed by the individual gauge for localized orbitals method, dissect pi effects from the sigma single bonds and lone pair influences. CnSn(2-) (n = 3-5) structures in Dnh symmetry are minima. Their aromaticity decreases with increasing ring size. C3S3(2-) is both sigma and pi aromatic, while C4S4(2-) and C5S5(2-) are much less aromatic. NICS(0)pi, the C-C(pi) contribution to NICS(0) (i.e., at the ring center), decreases gradually with ring size. In contrast, cyclic C6S6(2-) prefers D2h symmetry due to the balance between aromaticity, strain energy, and the S-S bond energies and is as aromatic as benzene. The theoretical prediction that C6S6(6-) has D6h minima was confirmed by X-ray structure analysis. Comparisons between thiocarbons and oxocarbons based on dissected NICS analysis show that CnSn(2-) (n = 3-5) and C6S6(6-) are less aromatic in Dnh symmetry than their oxocarbon analogues.

show abstract

Tetrathioquadratat, C ₄ S, ein vielseitiger Ligand in Metallkomplexen, II

Abstract: Tetrathioquadratat tritt in den Komplexen (Ph3P)2MC4S4M (PPh3)

Cited by 23 publications

References 43 publications

A novel series of rhenium-bipyrimidine complexes: synthesis, crystal structure and electrochemical properties

A novel series of rhenium-bipyrimidine complexes: synthesis, crystal structure and electrochemical properties

On the Prospects of Polynuclear Complexes with Acetylenedithiolate Bridging Units

A Theoretical and Structural Investigation of Thiocarbon Anions

Contact Info

Product

Resources

About

Tetrathioquadratat, C 4 S, ein vielseitiger Ligand in Metallkomplexen, II

Abstract: Tetrathioquadratat tritt in den Komplexen (Ph3P)2MC4S4M (PPh3)

Cited by 23 publications

References 43 publications

A novel series of rhenium-bipyrimidine complexes: synthesis, crystal structure and electrochemical properties

A novel series of rhenium-bipyrimidine complexes: synthesis, crystal structure and electrochemical properties

On the Prospects of Polynuclear Complexes with Acetylenedithiolate Bridging Units

A Theoretical and Structural Investigation of Thiocarbon Anions

Contact Info

Product

Resources

About

Tetrathioquadratat, C ₄ S, ein vielseitiger Ligand in Metallkomplexen, II