The reaction of CpRu(PPh3)2+ with trimethylenesulfide. Synthesis and molecular and crystal structure of [CpRu(PPh3)2(SC3H6)]CF3SO3

Park, Haengsoon; Draganjac, M.; Scott, Syrona R.; Cordes, A. W.; Eggleton, Gordon L.

doi:10.1016/0020-1693(94)03952-6

Cited by 7 publications

(3 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…S(4)-B(9) at 1.885 (5) and S(6)-B(7) at 1.889(6) A ˚. Also noteworthy is that the range of S-B distances in compound 4, from 1.884(5) to 1.936(5) A ˚, was similar to those observed for compound 9, 1.880 (10) An additional noteworthy point is the location of the endoterminal hydrogen atom on B(8) in compound 4. This is as found for many analogues such as the 4-L-arachno-B 9 H 13 series that have all-boron clusters, in which L is a two-electron donor ligand in the equivalent position to that of PMePh 2 in compound 4.…”

Section: Crystal and Molecular Structuressupporting

confidence: 60%

“…Crystal Data. C 23 H 33 B 6 PRuS 2 , M = 570.51, monoclinic, P2 1 /c, a = 11.0430 (10), b = 10.1578 (7), c = 24.528(2) A ˚, b = 94.168(7) • , Z = 4, D x = 1.381 g cm −3 , U = 2744.1(4) A ˚3, F(000) = 1168, k(Mo-Ka) = 0.7107 A ˚, l = 0.793 mm −1 , T = 294(1) K, R = 0.0432 for 4115 observed reflections, R w = 0.1036 for all 6264 unique reflections. Boron cage H atoms were located from a difference synthesis and their coordinates normalised to give a B-H distances of 1.10 A ˚; these H atom contributions were then included but not refined in the final calculations.…”

Section: X-ray Analysis Of [5-(p-cym)-8-(ph 2 Mepmentioning

confidence: 99%

See 1 more Smart Citation

Coordination and cluster compounds of ruthenium with the [hypho-1,2-S2B6H9]– ligand

Ferguson¹,

Gallagher

Kennedy

et al. 2005

Dalton Trans.

View full text Add to dashboard Cite

The reaction between [tmndH][hypho-1,2-S(2)B6H9](tmnd =N,N,N',N'-tetramethylnaphthalene-1,8-diamine) and [RuCl(PPh3)2(eta5-Cp)] in CH2Cl2 at room temperature afforded two ruthenathiaboranes, [5-(eta(5)-Cp)-5-(PPh3)-5,4,6-RuS2B6H9], 1, and [Ru(eta(1)-1,2-S2B6H9)(PPh3)2(eta5-Cp)], 2, in 6 and 48% yields, respectively. The heating of a solution of [Ru(eta(1)-1,2-S2B6H9)(PPh3)2(eta5-Cp)] 2 in CH2Cl2 at reflux temperature afforded 1 in 59% yield. Compound 1 could be described as either a hypho nine-vertex {RuS2B6} cluster or a coordination compound of ruthenium which contains a bidentate eta2-dithiaborate cluster ligand; the latter description is preferred. Compound 2 contains an eight-atom hypho-type {1,2-S2B6} cage bonded to the ruthenium atom of the {Ru(PPh3)2(eta5-Cp)} unit by one sulfur atom and may be described as a compound of ruthenium coordinated eta(1)- to the dithiaborate cluster ligand. The reaction between [tmndH][hypho-1,2-S2B6H9] and [RuCl2(eta6-MeC6H4Pri)]2 in CH2Cl2 at room temperature afforded [5-(eta6-MeC6H4Pri)-arachno-5,4,6-RuS2B6H8], 3, in 94% yield. Further reaction of 3 and PMePh2 afforded another arachno{RhS2B6}cluster, [5-(eta6-MeC6H4Pri)-8-(PMePh2)-arachno-5,4,6-RuS2B6H6], 4, in 25% yield. Compounds 1, 2, and 4 were characterised with single crystal X-ray analyses.

show abstract

Section: Crystal and Molecular Structuressupporting

confidence: 60%

Section: X-ray Analysis Of [5-(p-cym)-8-(ph 2 Mepmentioning

confidence: 99%

Coordination and cluster compounds of ruthenium with the [hypho-1,2-S2B6H9]– ligand

Ferguson¹,

Gallagher

Kennedy

et al. 2005

Dalton Trans.

View full text Add to dashboard Cite

show abstract

“…In the ligand the C-S distances are 1.83(2) and 1.85(2) A15 and 1.823(8) and 1.828(9) A. 16 Thietane ligands undergo transformations involving C-H bond cleavage at the ring carbon atom at the 3-position. These transformations can be blocked by the placement of methyl groups at the 3-position.…”

Section: Terminally Coordinated Thietane Ligandsmentioning

confidence: 99%

The Chemistry of Thietane Ligands in Polynuclear Metal Carbonyl Complexes

Adams¹,

Falloon²

1995

Chem. Rev.

View full text Add to dashboard Cite

Thietane and Selenetane Complexes by Thermal Cycloaddition of Vinyl Ethers to Transition‐Metal‐Coordinated Thio‐ and Selenoaldehydes – Crystal Structure of Pentacarbonyl(7‐phenyl‐2‐oxa‐8‐thiabicyclo[4.2.0]octane‐S)tungsten(0)

1996

View full text Add to dashboard Cite

Pentacarbonyl(thiobenza1dehyde)tungsten und pentacarbonyl(selenobenza1dehyde)tungsten ( l a and l b ) undergo a thermal [2 + 21 cycloaddition with several vinyl ethers to give highly substituted transition metal-coordinated thietanes and selenetanes. The addition is highly regio-and stereospecific. The products undergo acid-catalyzed rearrangements, which lead to thermodynamically more stable diastereomers of the Thio-and selenoaldehydes not stabilized by either bulky substituents or by conjugation with heteroatoms like nitrogen or sulfur are unstable and immediately oligomerize['"pt~. The high reactivity considerably restricts the use of thio-and selenoaldehydes as building blocks in organic synthesis. Until now, only inter-[2a-e] or intramolecular [3aa,b] [4 + 21 cycloadditions with conjugated dienes and ene reactions are known. In these reactions the heteroaldehydes are generated in situ. One way to circumvent the problems connected with the high reactivity of thio-and selenocarbonyl compounds is to use their transition metal complexes [4]. In the past decade, we successfully employed pentacarbonyl(thiobenza1dehyde)tungsten complexes [5] in cycloaddition reactions with electron-rich alkynes[""-"] and die n e~[~~-~] and observed a similar reactivity pattern for the analogous selenobenzaldehyde Recently, cationic thiobcnzaldehyde complexes of ruthenium, [(q5-C5H5)(P-P)Ru{S=C(C6H4R)H}]+ (P-P = dppe, dppm, dmpe; R = H, CI, OMe), were also used as starting compounds in cycloaddition reactions with cyclopentadiene and 2,3-dimethylb~tadiene[~~.~I.We now report on (a) the reactions of thiobenzaldehyde and selenobenzaldehyde complexes with vinyl ethers, (b) a study of the isomerization of the kinetically controlled reaction product containing a fimr-membered heterocycle to its more stable isomer and (c) an X-ray structural analysis of a thietane tungsten complex. A preliminary account of part of this work as well as a kinetical investigation of the cycloaddition reaction have appeared['".' l]. Results and DiscussionWhen a solution of pentacarbonyl(thiobenza1dehydc)-tungsten (la)"' in dichloromethane was treated with an exthietanes and selenetanes. The stereochemistry of both addition and rearrangement was established by reaction of deuterium-labeled vinyl ethers and by reaction of the cis and trans isomers of ethyl propenyl ether. The crystal structure of the bicyclic addition product of l a and 3,4-dihydro-2H-pyran is reported.cess of ethyl vinyl ether, the dark violet solution turned redbrown within several hours. Since l a slowly decomposes in solution at ambient temperature, the reaction had to be carried out at -30°C. Column chromatography of the reaction products on silica gel afforded the thietane complex 3a (Scheme 1) as a yellow oil. The structure of 3a was established by spectroscopic means. According to the IR spectrum of the yellow oil the pentacarbonyl tungsten fragment is still present in the isolated compound. The elemental analysis and the mass spectrum both indicated a 1 : 1 adduct of l a and the v...

show abstract

The reaction of CpRu(PPh3)2+ with trimethylenesulfide. Synthesis and molecular and crystal structure of [CpRu(PPh3)2(SC3H6)]CF3SO3

Cited by 7 publications

References 16 publications

Coordination and cluster compounds of ruthenium with the [hypho-1,2-S2B6H9]– ligand

Coordination and cluster compounds of ruthenium with the [hypho-1,2-S2B6H9]– ligand

The Chemistry of Thietane Ligands in Polynuclear Metal Carbonyl Complexes

Thietane and Selenetane Complexes by Thermal Cycloaddition of Vinyl Ethers to Transition‐Metal‐Coordinated Thio‐ and Selenoaldehydes – Crystal Structure of Pentacarbonyl(7‐phenyl‐2‐oxa‐8‐thiabicyclo[4.2.0]octane‐S)tungsten(0)

Contact Info

Product

Resources

About