Mixed-ligand complexes of rhenium I. The reaction of ReNCl2(Me2PhP)3 with bidentate chelate ligands. X-ray crystal structures of chloroN-(N,N-diethylthiocarbamoyl)-benzamidinato]bis(dimethylphenylphosphine)nitridorhenium(V), [ReN(Cl)(Me2PhP)2(Et2tcb)], and {bis(μ-ethyldithiophosphato-S, S′, O) di[bis(dimethylphenylphosphine)nitridorhenium(V) ]}, [ReN(Me2PhP)2Etdtp)]2

Abram, Ulrich; Ritter, Simone

doi:10.1016/s0020-1693(00)82829-7

Cited by 32 publications

(8 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Only three crystal structure studies could be located, but only one, that of [(Ph 2 PC 2 H 4 AsPh 2 )Ni(S 2 P(O)OMe)], contains the appropriate bidentate RO(O)PS 2 2- ligand. The other two include [(NC) 2 C 2 S 2 Ni(S 2 P(OH)OEt)] - which contains a monoanionic, acid ligand, EtO(HO)PS 2 - , and [(Me 2 PhP) 4 Re 2 N 2 (S 2 P(O)OEt) 2 ], which contains EtO(O)PS 2 2- as a bridging, tridentate ( S , S ‘, O ) ligand. Restricting therefore to the case of [(Ph 2 PC 2 H 4 AsPh 2 )Ni(S 2 P(O)OMe)], comparison to the present structure of EtS{Mo 2 (PO)}SEt 4 shows the RO(O)PS 2 2- ligands to be very similar.…”

Section: Resultsmentioning

confidence: 99%

“…With specific regard to dithiophosphates, these ligands tend to be fairly inert and few examples of de-esterification have been well characterized. The well-defined examples include as products [(Ph 2 PC 2 H 4 (As,P)Ph 2 )Ni(S 2 P(O)OMe)], [(NC) 2 C 2 S 2 Ni(S 2 P(OH)OEt)] - , [(Me 2 PhP) 4 Re 2 N 2 (S 2 P(O)OEt) 2 ], [(R 3 P) 2 M(S 2 P(O)OR‘)] (M = Pd, Pt), and [(Ph 2 PC 2 H 4 (As,P)Ph 2 )Co(S 2 P(OMe) 2 )(S 2 P(O)OMe)] . Except for [(NC) 2 C 2 S 2 Ni(S 2 P(OH)OEt)] - , whose mechanism of formation was not evident, the other products conceivably arose from nucleophilic attack on a bound (RO) 2 PS 2 - ligand.…”

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Activation of Ligand Reactivity: Thiolate C−S and Dithiophosphate Ester C−O Heterolyses within a Dimolybdenum(V) System

et al. 1999

View full text Add to dashboard Cite

Ligand reactivity was demonstrated for sulfide alkylation, thiolate dealkylation, and dithiophosphate de-esterification within molybdenum(V) dimers. The cationic complex [Mo(2)(NC(6)H(4)Me)(2)(S(2)P(OEt)(2))(2)(&mgr;-O(2)CMe)(&mgr;-SR)(2)](+) was inductively activated toward thiolate C-S and dithiophosphate C-O heterolyses. The dealkylations were studied using anionic nucleophiles, and various reactivity patterns were characterized. The de-esterification of the diethyl dithiophosphate ligands produced complexes containing the rare monoester EtO(O)PS(2)(2)(-) ligand. This ligand's phosphoryl group was poorly nucleophilic but weakly basic. Crystallographic comparisons between the activated cation and the neutral complex [Mo(2)(NC(6)H(4)Me)(2)(S(2)P(OEt)(2))(2)(&mgr;-O(2)CMe)(&mgr;-S)(&mgr;-SMe)] were conducted to delineate structural differences related to the activation. A crystallographic study was also done of the complex [Mo(2)(NC(6)H(4)CH(3))(2)(S(2)P(OEt)(2))(S(2)P(O)OEt)(&mgr;-O(2)CMe)(&mgr;-SEt)(2)], which provided internal comparison of monoester EtO(O)PS(2)(2)(-) and diester (EtO)(2)PS(2)(-) ligand types.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Activation of Ligand Reactivity: Thiolate C−S and Dithiophosphate Ester C−O Heterolyses within a Dimolybdenum(V) System

et al. 1999

View full text Add to dashboard Cite

show abstract

“…The geometry of the molecule is, thus, directly comparable with rhenium complexes of the general composition [ReN(Cl)-(PPhMe 2 ) 2 L] where L represents dialkyldithiocarbamate 16 or N,NЈ-dialkylthiocarbamoylbenzamidinate. 14 The exceptionally long Tc᎐Cl bond is due to the trans labilizing influence of the multiply bonded nitride ligand. The bonding situation in [TcN(Cl)(PPhMe 2 ) 2 {N(SPPh 2 ) 2 }] therefore comes close to that in the analogous rhenium complex [ReN(Cl)(PPhMe 2 ) 2 -{N(SPPh 2 ) 2 }], the crystal structure of which has been published elsewhere.…”

Section: Resultsmentioning

confidence: 99%

Technetium(V) and rhenium(V) nitrido complexes with bis(diphenyl-thiophosphoryl)amide, N(SPPh2)2−

Abram¹,

Lang²,

Abram³

et al. 1997

J. Chem. Soc., Dalton Trans.

Self Cite

View full text Add to dashboard Cite

“…Compounds 6 are represented by BnS{Mo 2 (PO)}SOEt; in addition to the thioperoxide ligand, this compound also provides another structural characterization of a dianionic, monoalkyl dithiophosphate ligand. The additional interest therein lies in the fact that there are few structural studies known for this ligand, − in stark contrast to the extensive characterization of monoanionic, dialkyl dithiophosphate ligands.…”

Section: Resultsmentioning

confidence: 99%

Alkylation of a Dimolybdenum SO Bridge, Subsequent Reactions, and Characterization of the Thioperoxide Bridge

et al. 2009

View full text Add to dashboard Cite

The SO bridge of the complex, [Mo(2)(NTo)(2)(S(2)P(OEt)(2))(2)(mu-O(2)CMe)(mu-SBn)(mu-SO)], 1, displayed nucleophilicity at O, giving alkylation products [Mo(2)(NTo)(2)(S(2)P(OEt)(2))(2)(mu-O(2)CMe)(mu-SBn)(mu-SOR)](+), 4(+), which contained the thioperoxide bridge. These cations were then subject to nucleophilic attack by two pathways. Debenzylation of the bridge thiolate in 4(+) afforded neutral [Mo(2)(NTo)(2)(S(2)P(OEt)(2))(2)(mu-O(2)CMe)(mu-S)(mu-SOR)], 5; de-esterification of a dithiophosphate ligand in 4(+) gave [Mo(2)(NTo)(2)(S(2)P(O)(OEt))(S(2)P(OEt)(2))(mu-O(2)CMe)(mu-SBn)(mu-SO)], 6, which contained a monoester, dithiophosphate ligand. Complex 1 gave a slow and clean reaction in the crystalline state, further demonstrating its nucleophilicity by attacking a neighboring molecule in its lattice. X-ray crystallography confirmed the thioperoxide linkage and revealed structural similarities of the Mo(2)(mu-SOR) unit to sulfenate esters (RSOR) and related derivatives.

show abstract

Cited by 32 publications

References 11 publications

Activation of Ligand Reactivity: Thiolate C−S and Dithiophosphate Ester C−O Heterolyses within a Dimolybdenum(V) System

Activation of Ligand Reactivity: Thiolate C−S and Dithiophosphate Ester C−O Heterolyses within a Dimolybdenum(V) System

Technetium(V) and rhenium(V) nitrido complexes with bis(diphenyl-thiophosphoryl)amide, N(SPPh2)2−

Alkylation of a Dimolybdenum SO Bridge, Subsequent Reactions, and Characterization of the Thioperoxide Bridge

Contact Info

Product

Resources

About