P-Bonded disulfur. Structure of disulfurbis(bis(diphenylphosphino)ethane)iridium(I) chloride. acetonitrile

Bonds, Wesley D.; Ibers, James A.

doi:10.1021/ja00765a026

Cited by 49 publications

(14 citation statements)

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“…1), which can act as tridentate ligands, are bonded by the S atoms, formingoa disulfide bridge. The S(1)---S(2) distance is 2.041 (2)A; this is in good agreement with disulfide bonds reported for analogous structures (Bonds & Ibers, 1972;Riley & Serf, 1972;Kessissoglou, Butler & Pecoraro, 1987;Sellmann, Prechtel, Knoch & Moll, 1993). The most interesting feature of this structure is the significant twist of A relative to B.…”

supporting

confidence: 85%

N,N'-[Dithiobis(o-phenylene)]bis(2-hydroxy-1-naphthaldimine)

Elmalı¹,

Özbey²,

Kendi³

et al. 1995

Acta Crystallogr C

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supporting

confidence: 85%

N,N'-[Dithiobis(o-phenylene)]bis(2-hydroxy-1-naphthaldimine)

Elmalı¹,

Özbey²,

Kendi³

et al. 1995

Acta Crystallogr C

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“…In contrast to the synthesis of 4, complexes 5 were produced without any other platinum products, but the differences in reactivity of 3 toward sulfur and selenium are unclear at present. The E1ÀE2 bond lengths and the E1-Pt1-E2 bond angles of the PtE 2 (E S, Se) rings are similar to those of other ME 2 complexes, for example, [IrS 2 (dppe) 2 ] 2.066(6) ä, 50.8(2)8, [18] [Ru 2 (CO) 2 (m-CO)(m-S)(S 2 )(m-dppm) 2 ] 2.13(1) ä, 51.8(3)8, [19] [(TpTP)TiS 2 ] 2.042(3) ä, 52.79(9)8 (TpTP tetra-p-tolylporphyrin), [20] [Os-Se 2 (CO) 2 (PPh 3 ) 2 ] 2.321(1) ä, 54.23(2)8, [21] and [IrSe 2 (dppe) 2 ] 2.312(3) ä, 54.3(1)8. [17] Crystallographic analysis showed that 4 b and 5 b are isomorphous and their geometries are very similar.…”

supporting

confidence: 71%

The First Disulfur and Diselenium Complexes of Platinum: Syntheses and Crystal Structures

2002

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“…23 (2)O, the C-Os-C angle is 94.6 (3)'. The Os atom and the C O ligands form the equatorial plane, whereas values of 2.34 (2) and 2.34…”

Section: Resultsmentioning

confidence: 99%

Preparation and reactivity of some .eta.2-S2 and .eta.2-Se2 complexes of osmium and the x-ray crystal structure of Os(.eta.2-Se2)(CO)2(PPh3)2

Farrar¹,

Grundy²,

Payne³

et al. 1979

J. Am. Chem. Soc.

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Payne, Walker, et al. r 2 -S z and r2-Se2 Complexes of Osmium 6511 (19) It could be argued that the absence of emission from 'HD' and 'H2D2+ arises from efficient bimolecular quenching of these species by D. This possibility is ruled out by the low concentrations employed. Either the quenching constants required to produce our observed results would have to exceed IO1* M-' s-', an impossibility, or the luminescencedecay curves of 'D would have to exhibit measurable rise times, which is not observed.(20) (&!$ -1) -1.05 and 7017 -1 -0.80 for Ru(phen)Z(CN) at 1.5 M HC104while the corresponding values are 0.27 and 0.18 at 1.5 M HCIOl for Ru(bpy)p(CN)z. (21) Alternative explanations of the appearance of the HD+ and H#+ emissions are (1) the media hinders equilibration of the excited state by decreasing k-1 and k-2 or (2) the media decreases the quenching component in k~s and k H~. We consider these possibilities unlikely. Only emission from D is seen in glasses composed of aqueous 12 M HCI or methanol-water HCI glasses even though only protonated species are excited. With the far stronger acid, H2S04, emissions of protonated species are seen, however, in methanol-water-sulfuric acid mixtures over a wide range in sulfuric acid and methanol concentrations. These possibilities would require either an enormous ability of the sulfuric acid media to suppress thermodynamically allowed excited-state deprotonation or a remarkable selectivity in the low-temperature media for deactivating one species in preference to another. To us the equilibrium maintenance of detectable amounts of 'HD+ and *H2D2+ at 77 K by the high acidity of these media is much more reasonable. (22) This statement is based on the assumption that the relative energies of the CT states are changing continuously relative to the 3(?r-'~) even foc a given species. This, in turn, causes large changes in the 3 (~-'~) component of the emitting state (eq 7). In view of the large solvatochromic shifts of the excited states of the complexes, this assumption seems quRe reasonable. Abstract:The compounds Os(q2-Se2)(CO)2(PPh3)2, Os(q2-Se2)(CO)(CNR)(PPh3)2 where R = p-tolyl, and Os(q2-S2)-(C0)2(PPh3)2 have been prepared. The reactivity of the (a2&) and (q2-Se2) ligands has been investigated and, in contrast to that of the (~~-0 2 ) analogues, which are oxidizing in character, has been found to be reducing in nature. Thus the ligands are readily attacked by alkylating agents to give cations of the type [Os(q2-Se2Me)(CO)2(PPh3)2]+ which react further with borohydride to yield complexes of the type Os(H)(q1-Se2Me)(CO)2(PPh3)2. Reaction with iodine or dinitrogen tetroxide yields the known complexes Osl2(C0)2(PPh3)2 and O S ( N O~)~( C O )~( P P~~)~, respectively, with elemental selenium or sulfur being liberated. Reactions involving electrophiles such as NO+ and RN2+ have been observed in which nitric oxide and nitrogen are evolved with elemental sulfur or selenium being deposited, followed by subsequent decomposition of the osmium residue in the absence of suitable ligan...

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P-Bonded disulfur. Structure of disulfurbis(bis(diphenylphosphino)ethane)iridium(I) chloride. acetonitrile

Cited by 49 publications

References 0 publications

N,N'-[Dithiobis(o-phenylene)]bis(2-hydroxy-1-naphthaldimine)

N,N'-[Dithiobis(o-phenylene)]bis(2-hydroxy-1-naphthaldimine)

The First Disulfur and Diselenium Complexes of Platinum: Syntheses and Crystal Structures

Preparation and reactivity of some .eta.2-S2 and .eta.2-Se2 complexes of osmium and the x-ray crystal structure of Os(.eta.2-Se2)(CO)2(PPh3)2

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