(N-Benzoyl-N′-phenylthiourea-κS)chlorido(η4-1,5-cyclooctadiene)rhodium(I)

Kotze, Paulo Gustavo; Roodt, Andreas; Venter, Johan A.; Otto, Stefanus

doi:10.1107/s1600536810029740

Cited by 6 publications

(7 citation statements)

References 14 publications

(20 reference statements)

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“…Thus, when a tri-substituted thiourea ligand [1-(acyl/aroyl)-3,3-(di-substituted)thiourea] is employed, the thiourea coordinates principally as a monoanionic bidentate ligand, whereas a di-substituted thiourea [1-(acyl/aroyl)-3-(monosubstituted)thiourea] coordinates only through its sulfur atom as a neutral monodentate ligand which is stabilized through intramolecular hydrogen bonding. [245] One of these hydrogen bonds ensures that the sulfur and oxygen atoms are in a mutual trans position, which stabilizes the molecule in such a way that bidentate coordination is prevented. In the tri-substituted variation, this intramolecular interaction is not possible, which enables the ligand to coordinate through its sulfur and oxygen atoms simultaneously.…”

Section: Metal Complexesmentioning

confidence: 99%

“…cis-[M(L-S,O) 2 ] Pt(II) and Pd(II) complexes of 1-(3,4,5-trimethoxybenzoyl)-3,3-diethyl thiourea undergo reversible photo-induced isomerization to the corresponding trans isomer upon irradiation with visible light in the 320-570 nm range [291]. Similarly, the simple compound 1-benzoyl-3-phenyl-thiourea (R 1 = R 2 = C 6 H 5 , R 3 = H) also acts as a monodentately neutral ligand through sulfur in [RhCl(C 8 H 12 )(C 14 H 12 N 2 OS)] [245]. The geometry of the coordination sphere is approximately square planar about the Rh(I) atom, with two bonds to the π-electrons of the 1,5-cyclooctadiene ligand, one bond to the Cl − ligand and one bond to the S atom of the thiourea ligand.…”

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confidence: 98%

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A review on the chemistry, coordination, structure and biological properties of 1-(acyl/aroyl)-3-(substituted) thioureas

Saeed

Flörke

Erben

2013

Journal of Sulfur Chemistry

192

123

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This review provides an overview of the chemistry, structure and potential applications of 1-(acyl/aroyl)-3-(mono-substituted) and 1-(acyl/aroyl)-3,3-(di-substituted) thioureas, with general formula R 1 C(O)N (1) HC(S)N (3) R 2 R 3 . In recent years, the title compounds have found extensive applications as ligands in coordination chemistry. The effect that nitrogen substituents exert on the intra-and intermolecular hydrogen-bonding interactions is discussed, including their role on the coordination properties displayed by these ligands. Novel applications of transition metal complexes bearing 1-(acyl/aroyl)-3-(mono-and di-substituted) thioureas are introduced. Biological aspects are also highlighted. As recently demonstrated, high-throughput screening assay and structure-activity analyses are feasible for this class of compounds. The chemical versatility of 1-(acyl)-3-(substituted) thiourea molecules and the derived metal complexes, together with the possibility of determining detailed structural properties, join biological applications in a promising interdisciplinary approach. The bibliography includes 382 references with emphasis on the literature appearing after 2007.

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Section: Metal Complexesmentioning

confidence: 99%

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confidence: 98%

A review on the chemistry, coordination, structure and biological properties of 1-(acyl/aroyl)-3-(substituted) thioureas

Saeed

Flörke

Erben

2013

Journal of Sulfur Chemistry

192

123

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“…All metal-ligand bond lengths are within expected ranges [1]. However, depending on the substituents of the ligand, we have also observed bidentate coordination [2].…”

Section: Discussionmentioning

confidence: 65%

Crystal structure of (N-benzoyl-N'-(2,4,6-trimethylphenyl)thiourea-κS)chlorido(η4-cycloocta-1,5-diene) rhodium(I), C25H30ClN2ORhS

Warsink

Roodt

Venter

et al. 2013

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialTo an acetone (2 mL) solution of [Rh(h 4 -1,5-cyclooctadiene)Cl] 2 (20 mg, 0.0405 mmol), N-benzoyl-N'-(2,4,6-trimethylphenyl)-thiourea [9] (20.8 mg, 0.0811 mmol) was added. The reaction mixture was vigorously stirred until all of the reagents were fully dissolved. The acetone was then allowed to evaporate slowly to obtain the product as an orange crystalline solid. DiscussionIn the title compound, the thiourea ligand shows monodentate coordination through its sulfur-atom, analogous with a structure earlier reported by us. All metal-ligand bond lengths are within expected ranges [1]. However, depending on the substituents of the ligand, we have also observed bidentate coordination [2]. This shows the versatility of this ligand class, and conversely the need for careful elucidation of the reaction products. We initially chose this ligand type in our research towards bidentate systems [3-5], but we were amazed about its rich coordination chemistry, that depends heavily on the reaction conditions and transition metal precursor [6]. Also, the use of the 1,5-cyclooctadiene ligand gives important information on the influence of the other ligands [7,8]. In the title structure, the rhodium adopts a slightly distorted square planar geometry. The structure is intramolecularly stabilized by hydrogen bonds, of which that between N1 and Cl1 stabilizes the coordination sphere (2.38(3) Å), and the one between N2 and O1 (2.06(3) Å) stabilizes the overall ligand conformation. Additionally, there is an intermolecular hydrogen bond interaction between the amide moieties (N2···O1' = 2.50(3) Å; ' = y-x, y-y, -z), creating dimeric structures.

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“…These ligands show exceptional coordination behaviour, being able to coordinate through their sulfur atom alone as a neutral monodentate ligand [5,6], through their sulfur and oxygen atoms as a monoanionic bidentate ligand [7], and as a monoanionic bidentate ligand through its sulfur and one of its nitrogen atoms (this work). This four-membered chelate ring has a very small bite angle of 63.06 (4)°, whereas the bite angle of the S,O-coordination mode is much closer to the preferred 90°for square planar coordination to rhodium(I) [8].…”

Section: Discussionmentioning

confidence: 98%

Crystal structure of bis(triphenylphosphine)(carbonyl)(N-benzoyl-N'-(2-methyl-4-hydroxyphenyl)thioureato-κS,κN)rhodium(I), C52H43N2O3P2RhS

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Roodt

Venter

et al. 2013

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialTo a cold DMF solution (5 mL) of [Rh(m-Cl)(CO) 2 ] 2 (30 mg, 0.1028 mmol) 2 equivalents of N-benzoyl-N'-(4-hydroxy-2-methylphenyl)thiourea were added [9]. After 4 minutes of stirring, ice-cold water was added to precipitate a dark-red solid. After isolating the solid, it was taken up in diethyl ether and treated with 4 equivalents of triphenylphosphine. The solvent was allowed to evaporate slowly, yielding the title compound as bright orange crystals. DiscussionIn our ongoing research in bidentate ligand systems, we have investigated the use of thiourea (tu) ligands for the synthesis of rhodium complexes, amongst others [1][2][3][4]. These ligands show exceptional coordination behaviour, being able to coordinate through their sulfur atom alone as a neutral monodentate ligand [5,6], through their sulfur and oxygen atoms as a monoanionic bidentate ligand [7], and as a monoanionic bidentate ligand through its sulfur and one of its nitrogen atoms (this work). This four-membered chelate ring has a very small bite angle of 63.06 (4)°, whereas the bite angle of the S,O-coordination mode is much closer to the preferred 90°for square planar coordination to rhodium(I) [8]. The coordination in the title compound can be described as distorted trigonal bipyrimidal, with the two triphenylphosphine ligands in the apical positions. Alternatively, the N,S-thioureato ligand can be considered as one donating moiety, in which case the complex can be described as distorted square planar. The rhodium-ligand bond lengths are all within expected ranges; the Rh-S and Rh-N bond lengths are 2.623(1) and 2.278(2) Å, respectively. The C-O bond length within the carbonyl ligand is 1.158(2) Å, while it is coordinated in an almost linear fashion, with a Rh1-C01-O1 angle of 176.9(2)°. The solid state structure is stabilized by both intra-and intermolecular hydrogen bonds. The intramolecular bond is between the N1 hydrogen and O2 (1.88(2) Å), whereas the intermolecular ones link two molecules together in a dimeric fashion from the phenolic hydrogen to the benzoyl oxygen (O2-H2···O3, 1.99 Å).

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(N-Benzoyl-N′-phenylthiourea-κS)chlorido(η⁴-1,5-cyclooctadiene)rhodium(I)

Cited by 6 publications

References 14 publications

A review on the chemistry, coordination, structure and biological properties of 1-(acyl/aroyl)-3-(substituted) thioureas

A review on the chemistry, coordination, structure and biological properties of 1-(acyl/aroyl)-3-(substituted) thioureas

Crystal structure of (N-benzoyl-N'-(2,4,6-trimethylphenyl)thiourea-κS)chlorido(η4-cycloocta-1,5-diene) rhodium(I), C25H30ClN2ORhS

Crystal structure of bis(triphenylphosphine)(carbonyl)(N-benzoyl-N'-(2-methyl-4-hydroxyphenyl)thioureato-κS,κN)rhodium(I), C52H43N2O3P2RhS

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