A reinvestigation of Paneth's violet compound. The synthesis of tetramethyldibismuthine

Ludwig, Edward G.

doi:10.1021/om00070a029

Cited by 42 publications

(34 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…0.203 85 (10) -0.061 42 (10) -0.058 34 (9) 0.386 04 (10) 0.404 80 (9) 0.235 65 (10) 0.136 4 (6) 0.109 3 (6) (3) 0.05445 (8) (8) 0.383 89 (6) -0.034 80 (8) 0.296 70 (6) 0.191 66 (8) 0.241 62 (6) 0.389 77 (8) 0.182 33 (6) 0.229 2 (5) 0.262 1 (4) 2.3 (2) 2.5 (2) 2.9 (2) 0.2 (2) -0.3 (2) 0.479 2 (5) 0.337 8 (4) 3.6 (2) 3.3 (3) 3.8 (2) 0.2 (2) -1.6 (2) 2.59 (3) (4) 3.24 (4) (2) 6.0 (4) 5.6 (4) 5.6 (4) 5.7 (4) 6.9 (5) 6.9 (5) 4.9 (4) 5.6 (4) 6.2 (4) 4.8 (4) 5.8 (4) 6.6 (5) 8.2 (6) 6.2 (4) 7.2 (5) 10.5 (7) 5.3 (4) 5.3 (4) 0.098 (3) 0.041 (2) 0.296 (3) (2) 4.1 (5) 3.8 ( 5 ) 4.0 (5) 5.2 (6) 4.7 (6) 3.6 (5) 4.0 (5) 3.6 (5) 4.0 (5) 4.8 (6) 5.0 (6) 2.7 (4) 4.9 (6) 3.2 (4) 7.5 (8) 4.5 (5) 4.5 (5) 3.9 (5) a The form of the anisotroDic thermal parameter is expl-1/4(h2a*2B(1,1) …”

Section: Positional and Thermal Parameters And Their Esds For Hos(cunclassified

“…The non-hydride-containing sulfidoosmium carbonyl cluster compounds are believed to be formed via this decomposition pathway. 3 (6) 119.2 (6) 88.3 (8) 149.2 (7) 172.6 (7) 97.4 (7) 91.9 (7) 111.9 (6) 158.9 (8) 82.6 (7) 53.6 (1) 161.5 (7) 100.4 (7) 95.8 (6) 81.9 (1) 102.3 (7) 163. Details of the mechanism of this mode of decomposition remain to be established; thus, these compounds will not be further described a t this time.3vlZV13 The formation of dibenzyl strongly implies a degradation process involving an homolysis of the carbon-sulfur bond in the phenylmethanethiolato ligand with formation of benzyl radicals and [HOs3(CO)lo(S)] radicals.…”

Section: Hos(co)(cc-s)(cc-s) 111mentioning

confidence: 99%

“…5 (8) 96.5 (1) 97.1 (2) 89.2 (7) 79.8 (8) 103.7 (1) 94.9 (7) 88 (1) 54.3 (1) 90.1 (1) 0~( 6 ) -0~( 2)-C( 3) 0~( 6 ) -0~( 2)-C(4) ( 8) C(8)-0~(4)-C (9) contact is between oxygen atoms of the carbonyl ligands, Compound IV was obtained in low yield (-2.5%) and was shown by an X-ray crystallographic analysis to be an isomer of compound 111. 86.8 (7) 83.4 (2) 87.5 (7) 175.1 (8) 169.5 (7) 100.2 (7) 89 (1) 56.8 (1) 51.9 (1) 129.4 (6) 121.9 (7) 51.5 (1) 86.2 (1) 119. Table V contains a list of final positional and thermal parameters.…”

Section: (5) a And Os(6)-s(2) = 2466 (4) A This Seems Tomentioning

confidence: 99%

“…Table V contains a list of final positional and thermal parameters. 1 ( 6 ) 91.2 (7) 96.5 (7) 173.4 (7) 89.7 ( 9 ) 54.1 (1) 117.4 (8) 146. The hexaosmium cluster consists of a central group of four metal atoms, Os(l), Os(2), Os (3), and Os (4), which are arranged in the shape of a slightly nonplanar rhombus, Os(l)-Os(2) = 2.883 (1) A and Os-(2)-0s(3) = 2.854 (1) A, and are similar to those in Os3-(CO),,, Os-Os = 2.877 (3) A.15 However, the Os(l)-Os (4) and Os(3)-Os(4) lengths at 2.959 (1) and 2.970 (1) A, respectively are significantly longer.…”

Section: (5) a And Os(6)-s(2) = 2466 (4) A This Seems Tomentioning

confidence: 99%

See 3 more Smart Citations

Cleavage of carbon-sulfur bonds in thiolato ligands in osmium carbonyl cluster compounds. The synthesis and structural characterization of H2Os6(CO)18(.mu.4-S)(.mu.3-S) and two isomers of H2Os6(CO)17(.mu.4-S)(.mu.3-S)

Adams¹,

Horváth²,

Mathur³

et al. 1983

Organometallics

View full text Add to dashboard Cite

According to the skeletal electron pair theory, Os(CO), groups donate two electrons for cluster bonding, and Os-(CO), groups donate zero.% With the assumption that t h e sulfido ligand serves as a four-electron donor, compound I1 has 14 electrons or seven electron pairs for cluster bonding. Seven electron pairs will provide a filled set of bonding orbitals for a polyhedron with six vertices, t h e octahedron. Accordingly the five metal atoms Os(l), Os(2), Os(4), Os(6), Os(7) and the sulfide ligand adopt the shape of an octahedron.T h e mechanism of t h e formation of I1 from I plus I11 is difficult to predict. Overall, there is a loss of five ligands, two of acetonitrile and three carbonyls, and an increase by five in the number of metal-metal bonds. T h e sulfido ligand actually serves as a four electron donor both in I and 11. T h e initial link between I and I11 is probably via formation of a coordinate bond between the sulfido ligand in I and a metal atom in I11 upon displacement of one of t h e acetonitrile molecules. Cluster coupling via the formation of sulfur-metal donor bonds has been observed previously"J2 and most notably in t h e formation of the cyclotrimer [ (p-H)zRu3(CO)s(p4-S)]3.14 One of t h e sulfido-bridged metal-metal bonds in I is then opened, and the sulfur-coordinated osmium atom in I11 enters into metal-metal bonding with I. It is not now possible to predict the sequence of the remaining steps which leads t o 11. Acknowledgment. We wish t o thank the National Science Foundation for support of this research through Grant No. CHE 80-19041 and t h e Alfred P. Sloan Foundation for a fellowship t o R.D.A. Registry No. I,

show abstract

Section: Positional and Thermal Parameters And Their Esds For Hos(cunclassified

Section: Hos(co)(cc-s)(cc-s) 111mentioning

confidence: 99%

Section: (5) a And Os(6)-s(2) = 2466 (4) A This Seems Tomentioning

confidence: 99%

Section: (5) a And Os(6)-s(2) = 2466 (4) A This Seems Tomentioning

confidence: 99%

See 2 more Smart Citations

Cleavage of carbon-sulfur bonds in thiolato ligands in osmium carbonyl cluster compounds. The synthesis and structural characterization of H2Os6(CO)18(.mu.4-S)(.mu.3-S) and two isomers of H2Os6(CO)17(.mu.4-S)(.mu.3-S)

Adams¹,

Horváth²,

Mathur³

et al. 1983

Organometallics

View full text Add to dashboard Cite

show abstract

“…Im Rahmen dieser Arbeiten gelang die Darstellung des Bis-dimethylbismutino-methans durch entsprechende Umsetzung einer Natriumdimethylbismutid-Lösung mit Dibrommethan. Dagegen führt die Reaktion von Alkalidialkylbismutiden mit 1,2-Dihalogenethan unter Ethylenabspaltung zu den entsprechenden Tetraalkyldibismutanen [2][3][4][5][6].…”

unclassified

Reaktionen von Natriumdimethylbismutid mit α, ω-Dibromalkanen und Halogenomethyl-trimethyl-metallanen (M = Si, Ge, Sn) / Reaction of Sodium-dimethyl-bismuthide with α, ω-Dibromoalkanes and Halogenomethyl-trimethyl-metallanes (M = Si, Ge, Sn)

Wieber

Rudolph

1988

Zeitschrift Für Naturforschung B

View full text Add to dashboard Cite

The bis(dimethylbismuth)alkanes (CH3)2Bi(CH2)nBi(CH3)2 (n = 3, 4, 5) were prepared by reaction of NaBi(CH3)2 in liquid ammonia with dibromoalkanes Br(CH2)„Br (n = 3, 4, 5). Thermolysis of bis(dimethylbismuth)butane and bis(dimethylbismuth)pentane leads to the cyclic compounds 1-methyl-bismacyclopentane and 1-methyl-bismacyclohexane. Reaction of NaBi(CH3)2 with halogenomethyl(trimethyl)metallanes XCH2E(CH3)3 ( E = Si, Ge, Sn; X = Hal) produce compounds of the type (CH3)2BiCH2E(CH3)3.

show abstract

Bismuth: Organometallic Chemistry

Whitmire

2005

Encyclopedia of Inorganic Chemistry

View full text Add to dashboard Cite

Bismuth readily forms a variety of tri‐ and pentavalent organic derivatives by the reactions of bismuth halides with Grignard, organolithium, organozinc, or organoaluminum reagents. Bismuth(III) triaryl compounds are readily oxidized by chlorine and bromine to triaryl dihalides, while iodine reacts to produce aryl bismuth iodides. Some organobismuth compounds are Lewis acidic, showing the ready formation of higher coordination number adducts with traditional ligands. A variety of organobismuth compounds with bismuth–bismuth and bismuth–transition metal bonds are described. Organobismuth(V) have found uses as selective oxidants and aryl transfer reagents.

show abstract

A reinvestigation of Paneth's violet compound. The synthesis of tetramethyldibismuthine

Cited by 42 publications

References 0 publications

Cleavage of carbon-sulfur bonds in thiolato ligands in osmium carbonyl cluster compounds. The synthesis and structural characterization of H2Os6(CO)18(.mu.4-S)(.mu.3-S) and two isomers of H2Os6(CO)17(.mu.4-S)(.mu.3-S)

Cleavage of carbon-sulfur bonds in thiolato ligands in osmium carbonyl cluster compounds. The synthesis and structural characterization of H2Os6(CO)18(.mu.4-S)(.mu.3-S) and two isomers of H2Os6(CO)17(.mu.4-S)(.mu.3-S)

Reaktionen von Natriumdimethylbismutid mit α, ω-Dibromalkanen und Halogenomethyl-trimethyl-metallanen (M = Si, Ge, Sn) / Reaction of Sodium-dimethyl-bismuthide with α, ω-Dibromoalkanes and Halogenomethyl-trimethyl-metallanes (M = Si, Ge, Sn)

Bismuth: Organometallic Chemistry

Contact Info

Product

Resources

About