Novel Metalloreagent Cp(CO)2FeP(Se)(OR)2 Produced from P−Se Bond Cleavage in the Thermal Reaction of [CpFe(CO)2]2 with Phosphor-1,1-diselenolates

Liu, C. W.; Chen, Jem-Min; Santra, Bidyut Kumar; Wen, Sung-Yin; Liaw, Ben-Jie; Wang, Ju‐Chun

doi:10.1021/ic061538u

Cited by 9 publications

(19 citation statements)

References 26 publications

(16 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Previously, a 113 Cd chemical shift of 250 ppm was obtained for a cadmium(II) selenocarboxylate complex with trigonal bipyramidal CdSe 3 O 2 coordination geometry in CH 2 Cl 2 at 193 K . A CSD survey did not show any crystalline compound with CdSe 2 O 4 coordination, only one Cd(II) complex with CdSe 2 O 3 coordination, and one monomeric CdSe 3 O complex with the Cd–Se bond distances within 2.590–2.603 Å and Cd–OH 2 at 2.307 Å …”

Section: Discussionmentioning

confidence: 97%

Cadmium(II) Complex Formation with Selenourea and Thiourea in Solution: An XAS and ¹¹³Cd NMR Study

2012

View full text Add to dashboard Cite

The complexes formed in methanol solutions of Cd(CF3SO3)2 with selenourea (SeU) or thiourea (TU), for thiourea also in aqueous solution, were studied by combining 113Cd NMR and X-ray absorption spectroscopy. At low temperature (~200 K) distinct 113Cd NMR signals were observed, corresponding to CdLn2+ species (n = 0 - 4, L = TU or SeU) in slow ligand exchange. Peak integrals were used to obtain the speciation in the methanol solutions, allowing stability constants to be estimated. For cadmium(II) complexes with thione (C=S) or selone (C=Se) groups coordinated in Cd(S/Se)O5 or Cd(S/Se)2O4 (O from MeOH or CF3SO3-) environments the 113Cd chemical shifts were quite similar, within 93-97 ppm and 189 – 193 ppm, respectively. However, the difference in the chemical shift for the Cd(SeU)42+ (578 pm) and Cd(TU)42+ (526 ppm) species, with CdSe4 and CdS4 coordination, respectively, shows less chemical shielding for the coordinated Se atoms than for S, in contrast to the common trend with increasing shielding in the order: O > N > Se >S. In solutions dominated by mono- and tetra-thiourea / selenourea complexes, their coordination and bond distances could be evaluated by Cd K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. At ~200 K and high excess of thiourea a minor amount (up to ~30%) of [Cd(TU)5-6]2+ species was detected by an upfield shift of the 113Cd NMR signal (up to 423 ppm) and an amplitude reduction of the EXAFS oscillation. The amount was estimated by fitting linear combinations of simulated EXAFS spectra for [Cd(TU)4]2+ and [Cd(TU)6]2+ complexes. At room temperature, [Cd(TU)4]2+ was the highest complex formed, also in aqueous solution. Cd L3-edge X-ray absorption near edge structure (XANES) spectra of cadmium(II) thiourea solutions in methanol were used to follow changes in the CdSxOy coordination at room temperature. The correlations found from the current and previous studies between 113Cd NMR chemical shifts and different Cd(II) coordination environments are generally useful for evaluating cadmium coordination to thione-containing or Se-donor ligands in biochemical systems or for monitoring speciation in solution.

show abstract

Section: Discussionmentioning

confidence: 97%

Cadmium(II) Complex Formation with Selenourea and Thiourea in Solution: An XAS and ¹¹³Cd NMR Study

2012

View full text Add to dashboard Cite

show abstract

“…All of the reactions were performed in oven-dried Schlenk glassware by using standard inert-atmosphere techniques. NH 4 Se 2 P(O i Pr) 2 and L were prepared according to the reported methods. The syntheses of [Hg 3 I 6 L 2 ], 3 , and [CdL 3 (H 2 O)](ClO 4 ) 2 , 11 , were reported earlier .…”

Section: Methodsmentioning

confidence: 99%

“…NH 4 Se 2 P(O i Pr) 2 and L were prepared according to the reported methods. The syntheses of [Hg 3 I 6 L 2 ], 3 , and [CdL 3 (H 2 O)](ClO 4 ) 2 , 11 , were reported earlier . Commercial Hg(ClO 4 ) 2 · x H 2 O, HgX 2 (X = Cl, Br, I) (99.9%), Cd(ClO 4 ) 2 ·5H 2 O, and CdX 2 (X = Cl, Br, I) (99.9%) were purchased from Strem.…”

Section: Methodsmentioning

confidence: 99%

“…Crystal data and selected bond lengths and angles for 1 , 2 , 4 − 6 are summarized in Tables and , while those for 8 − 10 are summarized in Tables and , respectively. Crystallographic data of 3 and 11 were reported previously …”

Section: Methodsmentioning

confidence: 99%

“…On the other hand, the report of L , the only structure containing a secondary selenophosphito [( i PrO) 2 PSe] − moiety, was possible because of its better stability achieved by P coordination on the iron carbonyl fragment, which is reminiscent of the better stability of the P-coordinated secondary phosphine selenide . The free Se end of L is capable of binding other metals to form heterometallic complexes, which afforded Fe(II)−Hg(II)/Cd(II) as well as Fe(II)−Cu(I)/Ag(I) heterometallic compounds, the only reported heterometallic structures containing a secondary phosphine selenide/selenophosphito unit to date. It is worth noting that only one compound, [{CpNi{(OMe) 2 PS} 2 } 2 Ni], is known to involve its lighter congener, that is, the secondary thiophosphito [(OR) 2 PS] − moiety.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Conjugate Base of a Secondary Phosphine Selenide [P(Se)(OⁱPr)₂]⁻as the Bridging Unit for the Construction of Heterometallic Fe(II)−Hg(II)/Cd(II) Complexes

Sarkar¹,

Wen²,

Wang³

et al. 2009

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

Reactions of perchlorate salts of Hg(II)/Cd(II) with [CpFe(CO)(2)P(Se)(O(i)Pr)(2)] (denoted as L) produced dicationic clusters [HgL(2)](ClO(4))(2), 1; [HgL(3)](ClO(4))(2), 2; and [CdL(3)(H(2)O)](ClO(4))(2), 11. However, the reactions of L with Hg(II)/Cd(II) halides yielded neutral complexes. For instance, HgI(2) produced [Hg(3)I(6)L(2)], 3, or [HgI(2)L(2)], 4, depending on the metal-to-ligand ratio used. Reaction of L with any of the Hg(II)/Cd(II) halides in a 1:1 ratio produced neutral clusters [HgX(mu-X)L](2) (M = Hg; X = Cl, 5; Br, 6; I, 7; M = Cd; X = Cl, 8; Br, 9; I, 10). Thus, variation of the M-to-L ratio made it possible for the formation of compounds with different metal/ligand stoichiometries only when ClO(4)(-) and I(-) salts of Hg(II) were used. Single-crystal X-ray crystallography revealed that two and three L units were connected to a Hg(II) via its Se atom in 1 and 2, respectively, whereas Hg(II) in 4 was connected to two "I" and two "L" units. An L (through its Se) and a terminal halogen were attached to each of the Hg(II)'s of the Hg(2)X(2) parallelogram core in 5 and 6. The cadmium complex 8, with a Cd(2)Cl(2) parallelogram core, was isostructural with the mercury complex 5. Although bonding and connectivity in 8 were similar to those in 9 and 10, the conformation of the bulky L ligands was unusually syn in 9 and 10, unlike the anti orientation in 5, 6, and 8. The syn conformation of L was also observed in compounds 1 and 2. Secondary interactions, namely, Se...Se interaction, the X...H-C type of H-bonding (X = halogen or Se), and pi-stacking, revealed in the structures played a role in determining the ligand conformation. The [P(Se)(O(i)Pr)(2)](-), the conjugate base of secondary phosphine selenide [HP(Se)(O(i)Pr)(2)], acted as a bridge with P bonded to Fe and Se bonded to Hg (or Cd) in these heterometallic clusters. Compound 5 further demonstrated a longer P-Se bond in the secondary phosphine selenide compared to that in isostructural, tertiary phosphine selenide metal complexes.

show abstract

Unexpected One‐Electron Oxidation of a Secondary Phosphite Selenide Cp(CO)₂FeP(Se)(OiPr)₂ by GaCl₃ and InCl₃ – Rare Examples of Di‐ and Triselenide Formation

et al. 2013

View full text Add to dashboard Cite

The reactions of the neutral phosphonoselenoate [Cp(CO)2FeP(Se)(OiPr)2] (1) with Lewis acids (GaCl3, InCl3) produce dicationic complexes [{Cp(CO)2FeP(OiPr)2}2Sen][GaCl4]2, [n = 2 (2), 3 (3)] and [{Cp(CO)2FeP(OiPr)2}2Sen][InCl4]2 [n = 2 (4), 3 (5)] in good yields; the complexes comprise an Se3 (or Se2) chain that bridges two FpP(OiPr)2 groups [Fp = Cp(CO)2Fe]. These compounds are the one‐electron oxidation products of secondary phosphite selenide 1 by group 13 (Ga, In) trichlorides. On the other hand, the reaction of GaCl3 with (iPrO)2PSe2– (dsep) yields only the Lewis adduct tris(O,O‐diisopropyldiselenophosphate)gallium (6). The 31P NMR spectrum of 6 at 183 K reveals that the gallium(III) center is surrounded by one chelating and two pendant dsep ligands, which is in line with the obtained X‐ray structure. In addition, the two‐electron oxidation of 1 leads to phosphite [Cp(CO)2FeP(O)(OiPr)2] formation.

show abstract

Novel Metalloreagent Cp(CO)₂FeP(Se)(OR)₂ Produced from P−Se Bond Cleavage in the Thermal Reaction of [CpFe(CO)₂]₂ with Phosphor-1,1-diselenolates

Abstract: The reaction of [CpFe(CO)2]2 with NH4Se2P(OR)2 yields a novel reagent Cp(CO)2FeP(Se)(OR)2, which has demonstrated coordination properties at the Se center to form heterometallic clusters as well as reactivity at the Se site toward C-based electrophiles.

Cited by 9 publications

References 26 publications

Cadmium(II) Complex Formation with Selenourea and Thiourea in Solution: An XAS and ¹¹³Cd NMR Study

Cadmium(II) Complex Formation with Selenourea and Thiourea in Solution: An XAS and ¹¹³Cd NMR Study

Conjugate Base of a Secondary Phosphine Selenide [P(Se)(OⁱPr)₂]⁻as the Bridging Unit for the Construction of Heterometallic Fe(II)−Hg(II)/Cd(II) Complexes

Unexpected One‐Electron Oxidation of a Secondary Phosphite Selenide Cp(CO)₂FeP(Se)(OiPr)₂ by GaCl₃ and InCl₃ – Rare Examples of Di‐ and Triselenide Formation

Contact Info

Product

Resources

About

Novel Metalloreagent Cp(CO)2FeP(Se)(OR)2 Produced from P−Se Bond Cleavage in the Thermal Reaction of [CpFe(CO)2]2 with Phosphor-1,1-diselenolates

Abstract: The reaction of [CpFe(CO)2]2 with NH4Se2P(OR)2 yields a novel reagent Cp(CO)2FeP(Se)(OR)2, which has demonstrated coordination properties at the Se center to form heterometallic clusters as well as reactivity at the Se site toward C-based electrophiles.

Cited by 9 publications

References 26 publications

Cadmium(II) Complex Formation with Selenourea and Thiourea in Solution: An XAS and 113Cd NMR Study

Cadmium(II) Complex Formation with Selenourea and Thiourea in Solution: An XAS and 113Cd NMR Study

Conjugate Base of a Secondary Phosphine Selenide [P(Se)(OiPr)2]−as the Bridging Unit for the Construction of Heterometallic Fe(II)−Hg(II)/Cd(II) Complexes

Unexpected One‐Electron Oxidation of a Secondary Phosphite Selenide Cp(CO)2FeP(Se)(OiPr)2 by GaCl3 and InCl3 – Rare Examples of Di‐ and Triselenide Formation

Contact Info

Product

Resources

About

Novel Metalloreagent Cp(CO)₂FeP(Se)(OR)₂ Produced from P−Se Bond Cleavage in the Thermal Reaction of [CpFe(CO)₂]₂ with Phosphor-1,1-diselenolates

Cadmium(II) Complex Formation with Selenourea and Thiourea in Solution: An XAS and ¹¹³Cd NMR Study

Cadmium(II) Complex Formation with Selenourea and Thiourea in Solution: An XAS and ¹¹³Cd NMR Study

Conjugate Base of a Secondary Phosphine Selenide [P(Se)(OⁱPr)₂]⁻as the Bridging Unit for the Construction of Heterometallic Fe(II)−Hg(II)/Cd(II) Complexes

Unexpected One‐Electron Oxidation of a Secondary Phosphite Selenide Cp(CO)₂FeP(Se)(OiPr)₂ by GaCl₃ and InCl₃ – Rare Examples of Di‐ and Triselenide Formation