Sulphur-containing metal complexes

Kruger, Gert J.; Lotz, Simon; Linford, Lorna; Dyk, Martie Van; Raubenheimer, Helgard G.

doi:10.1016/0022-328x(85)88096-7

Cited by 25 publications

(10 citation statements)

References 14 publications

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“…That is, in the first step, dialkyldithiophosphate and Fe 3 (CO) 12 in a 1:1 molar ratio afford the [2Fe2S] intermediate M1 , then one P–S bond cleavage forms sulfur dianion, the dianion attacks the main frame structure and converts it to a new anion frame M2 and gets equimolar dialkyldithiophosphate at same time, and they trap the Fe(CO) x together to afford 1 and 2 . Similar P–S bond cleavage was also reported in the reaction of Fe 2 (CO) 9 and Lawesson's reagent ( p ‐MeOC 6 H 4 PS 2 ) 2 . Details regarding this pathway still need to be further studied (Scheme ).…”

Section: Resultssupporting

confidence: 65%

“…Finally, a new type of trinuclear iron–sulfur clusters was prepared. The result was encouraged because the trinuclear cluster was observed with the P‐Fe and S–Fe bond formed by the P‐S activation, the activation of the P–S bond by Fe 3 (CO) 12 is unusual . In addition, the generated new complexes can be taken as an important supplement to the diversity of trinuclear Fe/S clusters.…”

Section: Introductionmentioning

confidence: 99%

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Unexpected Reaction of Fe₃(CO)₁₂ with Dialkyldithiophosphate: The Case of P–S Bond Activation

Gong

Liang

et al. 2019

Zeitschrift anorg allge chemie

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The reaction of Fe3(CO)12 with O,O′‐dialkyldithiophosphate diethylamine salts (RO)2P{S}SH·Et2NH (R = CH3, CH2CH3) resulted in the formation of trinuclear cluster complex {μ‐SP(OR)2Fe[S2P(OR)2)]S‐μ]}Fe2(CO)6 [R = CH3 (1), CH2CH3 (2)]. The two complexes were characterized by elemental analysis, FT‐IR, NMR (1H, 31P and 13C) spectroscopy, as well as by X‐ray diffraction analyses. Crystal structures reveal that one P–S bond is cleaved during the reaction, yielding the [2Fe2S] unit together with FePS3(CO)2. The other dialkyldithiophosphate coordinated with iron by S, S chelating model. The trinuclear cluster was observed with the P‐Fe and S–Fe bond formed by the P‐S activation. In addition, the electrochemical properties for complex 2 as an illustration was also studied by cyclic voltammetry in MeCN.

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Section: Resultssupporting

confidence: 65%

Section: Introductionmentioning

confidence: 99%

Unexpected Reaction of Fe₃(CO)₁₂ with Dialkyldithiophosphate: The Case of P–S Bond Activation

Gong

Liang

et al. 2019

Zeitschrift anorg allge chemie

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“…This can be ascribed to the different chemical environments of the protons in positions 3 and 6 and those in positions 4 and 5 with respect to the ^-coordinated carbon atoms of the benzene ring. Inconclusive evidence for the existence of the proposed mono- 9) S(l)-C( 9) 1.836 (9) 0(6)-C( 7) 1.475 (10) C( 6)-0(6) 1.331 (8) C(9)-C(10) 1.461 (12) C(10)-C(ll) 1.516 (12) x/a y/b zjc t/(eq)" Fe(l) 2952 ( 1) 752 (1) 8271 ( 1) 38(1) C(l) 4833 ( 5) 775 (2) 8045 ( 4) 53 (3) 0(1) 6057 ( 3) 792 ( 2) 7904 (3) 71 (2) C( 2) 3009 ( 4) 1237 (2) 9695 ( 3) 51 (3) 0(2) C( 4) 3979 ( 5) 2194 ( 2) 6981 ( 4) 51 (3) 0(4) 5149 ( 3) 2404 ( 2) 6905 ( 3) 72 (2) C( 5) 1447 ( 5) 2395 ( 2) 5782 ( 4) 52 (3) 0( 5) 1070 ( 4) 2681 (2) 4891 ( 3) 78 (2) C( 6) 2161 (5) 2598 ( 2) 8331 ( 4) 51 (3) 0( 6) 2227 (3) 3028 (…”

Section: Synthesismentioning

confidence: 99%

Use of organolithium reagents in the synthesis of diiron complexes with bridged and terminal carbene ligands. X-ray structures of [cyclic] (CO)3Fe{.mu.-C(OEt)-.eta.2-C6H4NMe2}Fe(CO)3 and [cyclic] (CO)3Fe{S(CH2)3S}Fe(CO)2{C(OEt)Ph}

Lotz¹,

Rooyen²,

Dyk³

1987

Organometallics

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499inversion of 3b ought to be nontrivial since the phosphorus atom in this compound is still four-coordinate. Without having further proof for this, we propose as an inversion pathway a rotation of the Fe-W unit around the FePW three-center bond, thereby formally considering . the phosphorus atom as three-coordinate. At the moment there is, however, no obvious way of testing this hypothesis. ConclusionsThe cluster types 1 and 2 extend the series of clusters that can be opened by addition of donor ligand^.^^'^^ They differ from the previously studied p3-PR-bridged trimetal systems in that they add two PR3 ligands showing no noticeable intermediate and that reversal to the closed cluster framework is possible by loss of CO only or by loss of CO and PR3. For the one case studied kinetically an associative mechanism is indicated for the rate-determining step in complete analogy to dinuclear FeCo(p-AsMe2) systems. A significant stereochemical information has been obtained in the observation that optical activity is maintained in this type of cluster opening but that the open cluster framework sustains slow inversion. This puts a serious limitation on the transfer of stereochemical in-formation in conversions that may involve cluster framework reactions.Although the cluster types 1 and 2 demonstrate again that ligand substitution on clusters can occur by an addition-elimination sequence, this will certainly not be the case for all custers. Future investigations should elucidate which factors (besides just metal-metal bond strengths) determine the preference of clusters for "internal" or "external" substitution mechanisms that in turn should offer a better understanding for the still ill-defined area of cluster catalysis.Acknowledgment. This work was supported by the Deutsche Forschungsgemeinschaft, the Alexander von Humboldt-Stiftung, and the Fonds der Chemischen Industrie. We thank Mr. C. de Meric de Bellefon and Mr. J.-L. Richert, Strasbourg, for NMR measurements, Dr. K. Steinbach, Marburg, for mass spectra, and the Rechenzentrum der Universiat Freiburg for computer time. Supplementary Material Available: Tables containing all distances and angles for 3a (7 pages); a listing of FJF, for 3a (13 pages). Ordering information is given on any current masthead Reaction of iron pentacarbonyl with o-MeXC6H4Li (X = 0, NMe), followed by alkylation of the acylmetalate with [Et30]BF4, gave the methylene-bridged complexes (C0)3Fe(p-C(OEt)-.r12-C6H4XMe)-Fe(C0)3. Substitution of two carbonyls from the complex where X = 0 with P(OMe)3 yielded (CO),-(P(OMe)3)Fe(~-C(OEt)-.r12-c~H4OMe)Fe(P(OMe)~)(CO)2 as the main product. The complexes (CO), F: (S(CH2)3S)Fe(CO)2(C(OEt)R) (R = n-Bu, Me, Ph), which have terminal carbene ligands, were synthesized from (CO)3Fe(S(CHz)3S)Fe(CO)3 and organolithium reagents. The structures of (CO),Fe(p-C-(OEt)-.r12-C6H4NMe2)Fe(CO)3 (11) and (CO)3Fe(S(CH2)3S)Fe(C0)2(C(OEt)Ph) (VII) were confirmed by X-ray crystallography. The crystals of I1 are monoclinic, space group PZ1/n, with a = 9.180 (3) A, b = 18.636 (4...

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“…The latter exists in equilibrium with 1 according to eq 4. 10 The compound [PhPS]318 is quite oxophilic, (MeCp)2TiS4(PAn)2 ^(MeCp)2TiS3(PAn) + l/3[AnPS]3 (4) and its solutions react quantitatively with Me2SO to give dimethyl sulfide and a soluble form of [PhPSO]". The same oligomer can also be prepared by treatment of [PhPS]3 with dry oxygen, and a spectroscopically similar material is formed through the reaction of [AnPS2]2 with acetamide (eq 5).19 Aerobic workup of solutions…”

Section: Resultsmentioning

confidence: 99%

Atom transfer and chelate fragmentation reactions of bis(cyclopentadienyl)titanium thiophosphoryls. Part 2

Zank¹,

Rauchfuss²

1986

Inorg. Chem.

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Sulphur-containing metal complexes

Cited by 25 publications

References 14 publications

Unexpected Reaction of Fe₃(CO)₁₂ with Dialkyldithiophosphate: The Case of P–S Bond Activation

Unexpected Reaction of Fe₃(CO)₁₂ with Dialkyldithiophosphate: The Case of P–S Bond Activation

Use of organolithium reagents in the synthesis of diiron complexes with bridged and terminal carbene ligands. X-ray structures of [cyclic] (CO)3Fe{.mu.-C(OEt)-.eta.2-C6H4NMe2}Fe(CO)3 and [cyclic] (CO)3Fe{S(CH2)3S}Fe(CO)2{C(OEt)Ph}

Atom transfer and chelate fragmentation reactions of bis(cyclopentadienyl)titanium thiophosphoryls. Part 2

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Sulphur-containing metal complexes

Cited by 25 publications

References 14 publications

Unexpected Reaction of Fe3(CO)12 with Dialkyldithiophosphate: The Case of P–S Bond Activation

Unexpected Reaction of Fe3(CO)12 with Dialkyldithiophosphate: The Case of P–S Bond Activation

Use of organolithium reagents in the synthesis of diiron complexes with bridged and terminal carbene ligands. X-ray structures of [cyclic] (CO)3Fe{.mu.-C(OEt)-.eta.2-C6H4NMe2}Fe(CO)3 and [cyclic] (CO)3Fe{S(CH2)3S}Fe(CO)2{C(OEt)Ph}

Atom transfer and chelate fragmentation reactions of bis(cyclopentadienyl)titanium thiophosphoryls. Part 2

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Unexpected Reaction of Fe₃(CO)₁₂ with Dialkyldithiophosphate: The Case of P–S Bond Activation

Unexpected Reaction of Fe₃(CO)₁₂ with Dialkyldithiophosphate: The Case of P–S Bond Activation