Reactivities of Secondary Phosphine Selenides Cp(CO)<sub>2</sub>FeP(Se)(OR)<sub>2</sub>: Formation of a Diiodine Charge Transfer Adduct and Se-Methylation

Chiou, Ling-Song; Fang, Ching‐Shiang; Sarkar, B. C.; Liu, Ling‐Kang; Leong, Max K.; Liu, C. W.

doi:10.1021/om900508b

Cited by 5 publications

(3 citation statements)

References 42 publications

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“…2.24(1) Å in P 4 Se 3 ), although substantially longer than the value expected for a PSe bond (cf. 2.117(2) Å in [FeCp{κ 1 P -P(Se)(OR) 2 }(CO) 2 ], while the Mo–Se lengths of ∼2.66 Å compare well with the value of 2.6897(4) Å measured in the related selenoacyl complex [Mo(η 2 -SeCR)(CO) 2 {HB(pz) 3 }] . Interestingly, two canonical forms involving either single or double Se–C bonds were proposed in the latter complex to account for the bonding within the corresponding MoCSe ring.…”

Section: Resultssupporting

confidence: 61%

Dimolybdenum Cyclopentadienyl Complexes with Bridging Chalcogenophosphinidene Ligands

Alvarez

Amor

et al. 2012

Inorg. Chem.

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The reactions of the phosphinidene-bridged complex [Mo(2)Cp(2)(μ-PH)(η(6)-HMes*)(CO)(2)] (1), the arylphosphinidene complexes [Mo(2)Cp(2)(μ-κ(1):κ(1),η(6)-PMes*)(CO)(2)] (2), [Mo(2)Cp(2)(μ-κ(1):κ(1),η(4)-PMes*)(CO)(3)] (3), [Mo(2)Cp(2)(μ-κ(1):κ(1),η(4)-PMes*)(CO)(2)(CN(t)Bu)] (4), and the cyclopentadienylidene-phosphinidene complex [Mo(2)Cp(μ-κ(1):κ(1),η(5)-PC(5)H(4))(η(6)-HMes*)(CO)(2)] (5) toward different sources of chalcogen atoms were investigated (Mes* = 2,4,6-C(6)H(2)(t)Bu(3); Cp = η(5)-C(5)H(5)). The bare elements were appropriate sources in all cases except for oxygen, in which case dimethyldioxirane gave the best results. Complex 1 reacted with the mentioned chalcogen sources at low temperature, to give the corresponding chalcogenophosphinidene derivatives [Mo(2)Cp(2){μ-κ(2)(P,Z):κ(1)(P)-ZPH}(η(6)-HMes*)(CO)(2)] (Z = O, S, Se, Te; P-Se = 2.199(2) Å). The arylphosphinidene complex 2 was the least reactive substrate and gave only chalcogenophosphinidene derivatives [Mo(2)Cp(2)(μ-κ(2)(P,Z):κ(1)(P),η(6)-ZPMes*)(CO)(2)] for Z = O and S (P-O = 1.565(2) Å), along with small amounts of the dithiophosphorane complex [Mo(2)Cp(2)(μ-κ(2)(P,S):κ(1)(S'),η(6)-S(2)PMes*)(CO)(2)], in the reaction with sulfur. The η(4)-complexes 3 and 4 reacted with sulfur and gray selenium to give the corresponding derivatives [Mo(2)Cp(2)(μ-κ(2)(P,Z):κ(1)(P),η(4)-ZPMes*)(CO)(2)L] (L = CO, CN(t)Bu), obtained respectively as syn (Z = Se; P-Se = 2.190(1) Å for L = CO) or a mixture of syn and anti isomers (Z = S; P-S = 2.034(1)-2.043(1) Å), with these diastereoisomers differing in the relative positioning of the chalcogen atom and the terminal ligand at the metallocene fragment, relative to the Mo(2)P plane. The cyclopentadienylidene compound 5 reacted with all chalcogens, and gave with good yields the chalcogenophosphinidene derivatives [Mo(2)Cp(μ-κ(2)(P,Z):κ(1)(P),η(5)-ZPC(5)H(4))(η(6)-HMes*)(CO)(2)] (Z = S, Se, Te), these displaying in solution equilibrium mixtures of the corresponding cis and trans isomers differing in the relative positioning of the cyclopentadienylic rings with respect to the MoPZ plane in each case. The sulfur derivative reacted with excess sulfur to give the dithiophosphorane complex [Mo(2)Cp(μ-κ(2)(P,S):κ(1)(S'),η(5)-S(2)PC(5)H(4))(η(6)-HMes*)(CO)(2)] (P-S = 2.023(4) and 2.027(4) Å). The structural and spectroscopic data for all chalcogenophosphinidene complexes suggested the presence of a significant π(P-Z) bonding interaction within the corresponding MoPZ rings, also supported by Density Functional Theory calculations on the thiophosphinidene complex syn-[Mo(2)Cp(2)(μ-κ(2)(P,S):κ(1)(P),η(4)-SPMes*)(CO)(3)].

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Section: Resultssupporting

confidence: 61%

Dimolybdenum Cyclopentadienyl Complexes with Bridging Chalcogenophosphinidene Ligands

Alvarez

Amor

et al. 2012

Inorg. Chem.

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“…As a result of this coordination, the PR*Se ligand formally provides the dimetal site with six electrons (two lone pairs from P and Se atoms and the π-bonding electrons of the P�Se double bond), which then becomes electron-precise (34 electrons) in agreement with the intermetallic length of 3.109(2) Å, consistent with the formulation of a Mo−Re single bond. 29 Besides this, we note that the P−Se separation of 2.241(5) Å in 7a is substantially longer than the P�Se distance in complex [FeCp{κ 1 P − P(Se)(OR) 2 }(CO) 2 ] (2.117(2) Å) 38 and instead approaches the reference value of ca. 2.27 Å for a single bond between these atoms.…”

Section: Stoichiometric Reactions Of Compounds 1 Withmentioning

confidence: 99%

Reactions of Heterometallic Phosphinidene-Bridged MoMn and MoRe Complexes with Sulfur and Selenium: From Chalcogenophosphinidene- to Trithiophosphonate-Bridged Derivatives

et al. 2023

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Reactions of [MoReCp(μ-PR*)(CO)6] with S8 were strongly dependent on experimental conditions (R* = 2,4,6-C6H2 t Bu3). When using 1 equiv of sulfur, complex [MoReCp(μ-η2:κ1 S-SPR*)(CO)6] was slowly formed at 313 K, with a thiophosphinidene ligand unexpectedly bridging the dimetal center in the novel μ-κ1 S:η2 coordination mode, as opposed to the μ-κ1 P:η2 mode usually found in related complexes. The latter underwent fast decarbonylation at 363 K to give [MoReCp(μ-η2:η2-SPR*)(CO)5], with a six-electron donor thiophosphinidene ligand rearranged into the rare μ-η2:η2 coordination mode. Depending on reaction conditions, reactions with excess sulfur involved the addition of two or three S atoms to the phosphinidene ligand to give new complexes identified as the dithiophosphinidene-bridged complex [MoReCp(μ-η2:κ2 S,S′-S2PR*)(CO)5], its dithiophosphonite-bridged isomer [MoReCp(μ-κ2 S,S′:κ2 S,S′-S2PR*)(CO)5], or the trithiophosphonate-bridged derivative [MoReCp(μ-κ2 S,S′:κ2 S,S′-S3PR*)(CO)5], all of them displaying novel coordination modes of their PRS2 and PRS3 ligands, as determined by X-ray diffraction studies. In contrast, the related MoMn complex yielded [MoMnCp(μ-η2:η2-SPR*)(CO)5] under most conditions. A similar output was obtained in reactions with gray selenium for either MoRe or MoMn phosphinidene complexes, which under different conditions only gave the pentacarbonyl complexes [MoMCp(μ-η2:η2-SePR*)(CO)5] (M = Re, Mn), these providing a new coordination mode for selenophosphinidene ligands.

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“…Selenium is another acceptor for X–X ··· A interactions that has been known for a long time. In 2009, the structure of an iron complex containing a phosphane selenide ligand was reported showing an I ··· Se contact (2.72 Å, 30 % reduction, QUDCEY)29 and an elongated I–I distance of 2.97 Å. More recently, eight structures in which Se is bonded to aromatic moieties as a bridging atom have been reported30 that also show I ··· Se interactions.…”

Section: Halogen Bonding With Organic Molecules In the Solid Statementioning

confidence: 99%

Alternative Motifs for Halogen Bonding

et al. 2013

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The halogen‐bonding interaction is one of the rising stars in supramolecular chemistry. Although other weak interactions and their influence on the structure and chemistry of various molecules, complexes and materials have been investigated thoroughly, the field of halogen bonding is still quite unexplored and its impact on chemistry in general is yet to be fully revealed. In principle, every Y–X bond (Y = electron‐withdrawing atom or moiety, X = halogen atom) can act as a halogen‐bond donor when the halogen is polarized enough by Y. Perfluorohalocarbons are iconic halogen‐bond donor molecules in which Y is a perfluorinated aryl or alkyl moiety and X is either iodine or bromine. In this article, alternative halogen‐bond motifs such as X2···A and Ar–X···A [A = Lewis basic halogen‐bond‐accepting atom of a molecule or ion; Ar = neutral or charged (hetero)aromatic system] are reviewed. In addition, haloalkenes, haloalkynes, N‐haloamides and other non‐metallic halogen‐bond donors and their respective halogen‐bonded structures will also be described. Although purely organic halogen‐bonding motifs are very prominent, the role of metal complexes in halogen bonding is becoming increasingly evident as well, which is also reflected in this review. Finally, halogen bonding in solution is briefly highlighted. Contemporary research is proving that halogen bonding is more than a solid‐state phenomenon and is now a well‐recognized weak interaction in chemistry.

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Reactivities of Secondary Phosphine Selenides Cp(CO)₂FeP(Se)(OR)₂: Formation of a Diiodine Charge Transfer Adduct and Se-Methylation

Cited by 5 publications

References 42 publications

Dimolybdenum Cyclopentadienyl Complexes with Bridging Chalcogenophosphinidene Ligands

Dimolybdenum Cyclopentadienyl Complexes with Bridging Chalcogenophosphinidene Ligands

Reactions of Heterometallic Phosphinidene-Bridged MoMn and MoRe Complexes with Sulfur and Selenium: From Chalcogenophosphinidene- to Trithiophosphonate-Bridged Derivatives

Alternative Motifs for Halogen Bonding

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Reactivities of Secondary Phosphine Selenides Cp(CO)2FeP(Se)(OR)2: Formation of a Diiodine Charge Transfer Adduct and Se-Methylation

Cited by 5 publications

References 42 publications

Dimolybdenum Cyclopentadienyl Complexes with Bridging Chalcogenophosphinidene Ligands

Dimolybdenum Cyclopentadienyl Complexes with Bridging Chalcogenophosphinidene Ligands

Reactions of Heterometallic Phosphinidene-Bridged MoMn and MoRe Complexes with Sulfur and Selenium: From Chalcogenophosphinidene- to Trithiophosphonate-Bridged Derivatives

Alternative Motifs for Halogen Bonding

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Reactivities of Secondary Phosphine Selenides Cp(CO)₂FeP(Se)(OR)₂: Formation of a Diiodine Charge Transfer Adduct and Se-Methylation