A novel nonacoordinate bridging selenido ligand in a tricapped trigonal-prismatic geometry. X-Ray structure of Cu11(μ9-Se)(μ3-Br)3[Se2P(OPri)2]6

Liu, C. W.; Hung, Chiu-Mine; Chen, Hsiu-Chih; Wang, Ju-Chung; Keng, Tai‐Chiun; Guo, K.

doi:10.1039/b005366j

Cited by 36 publications

(12 citation statements)

References 13 publications

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Section: Introductionmentioning

confidence: 77%

“…Four coordination modes of diselenophosphates have been identified in their metal complexes (II−V, Chart ), − and mode I is being reported for the first time in this paper. In view of our interest to develop coordination chemistry of diselenophosphates as ligands and also after finding very interesting polynuclear complexes with Cu I , Ag I , and Zn II , − we were curious to look into main group elements. In this respect, indium(III) formed octahedral, tris-chelated complexes, In[Se 2 P(OR) 2 ] 3 , which in solution state showed lability of the In−Se bonds, and in order to explore the generality of this observation, we were interested in investigating the interaction of dsep ligands with group 14 metals.…”

Section: Introductionmentioning

confidence: 77%

“…Diselenophosphates [dsep, Se 2 P(OR) 2 - ] have been known since 1968, but their coordination chemistry remained ignored, probably because of their oxidation and extrusion of Se from the ligand. − In the past decade Liu et al have demonstrated the novelty of diselenophosphates by studying their coordination chemistry, particularly with elements from groups 11−13, and by preparing several unusual clusters and polynuclear compounds. − There are only two structurally characterized compounds among elements other than groups 11−13, namely, [Mo 3 (μ 3 -Se)(μ 2 -Se 2 ) 3 {Se 2 P(OEt) 2 } 3 ](Br) 5 and Ni[Se 2 P(OEt) 2 ] 2 . In sharp contrast, many studies on compositions and structures of complexes of analogous phosphor-1,1-dithiolate ligands have been reported. − …”

Section: Introductionmentioning

confidence: 99%

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Syntheses, Structures, and VT NMR Studies of Diselenophosphates of Group 14 Organometals. DFT Calculations for Gas-Phase Stability of Dinuclear Ions, [(Ph₃M)₂{μ-Se, Se-P(OR)₂}]⁺(M = Ge, Sn, and Pb)

et al. 2005

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Equimolar reactions of group 14 compounds, (C 6 H 5 ) 3 MCl with (NH 4 )[Se 2 P(OR) 2 ], in diethyl ether yielded the first organometallic derivatives of diselenophosphates, viz., [Ph 3 M{η 1 -Se (Se)P(OR) 2 }] [M) Ge, R ) Et, i Pr, n Pr (1-3); Sn, Et, i Pr, n Pr (4-6); Pb, Et, i Pr, n Pr (7-9)]. The crystal structures of 1, 4, 6, and 7 showed that the geometry around a metal center for each compound is distorted tetrahedral. The (η 1 -Se) coordination mode with one pendant Se atom exhibited in these complexes is the new connective pattern for the diselenophosphates. 31 P and 77 Se NMR spectral studies reveal that whereas germanium compounds do not show lability of Ge-Se bonds, the Sn and Pb compounds do exhibit lability of Sn-Se and Pb-Se bonds, which involve exchange of the coordinated and pendant Se atoms at room temperature. This exchange process is slowed at low temperature and stopped at around 210 K. The exchange energy (∆G q ) is calculated to be in the range of 38-46 kJ mol -1 for compounds 4-9. Positive FAB-mass spectral data reveal that germanium compounds 1 and 3 have nearly equal abundance of molecular ions [(Ph 3 M){µ-Se, Se-P(OR) 2 }] + and dinuclear cations [(Ph 3 M) 2 -{µ-Se, Se-P(OR) 2 }] + ; the same is not true for tin and lead compounds 4, 5, 7, and 8, whose dinuclear cations are several times intense over their molecular ions. The structures of these dinuclear cations as well as their formation pathway have been studied by the density functional theory calculations.

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Section: Introductionmentioning

confidence: 77%

Section: Introductionmentioning

confidence: 77%

Section: Introductionmentioning

confidence: 99%

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Syntheses, Structures, and VT NMR Studies of Diselenophosphates of Group 14 Organometals. DFT Calculations for Gas-Phase Stability of Dinuclear Ions, [(Ph₃M)₂{μ-Se, Se-P(OR)₂}]⁺(M = Ge, Sn, and Pb)

et al. 2005

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“…The latter is frequently observed in dithiophosph(in)ate-stabilized M I 8 (M = Cu, Ag) cubic clusters encapsulating S 2– , Cl – , and Br – . Our research group has reported selenide- and halide-centered cubes, [Cu 8 (μ 8 -Se){Se 2 P(O i Pr) 2 } 6 ], [Ag 8 (μ 8 -Se){Se 2 P(O i Pr) 2 } 6 ], [Cu 8 (μ 8 -X){Se 2 P(OR) 2 } 6 ](PF 6 ), and [Ag 8 (μ 8 -X){Se 2 P(OR) 2 } 6 ](PF 6 ) (X = F, Cl, Br)…”

Section: Introductionmentioning

confidence: 99%

Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry

et al. 2020

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Structurally precise copper hydrides [Cu 11 H 2 {S 2 P(O i Pr) 2 } 6 (C≡CR) 3 ], (R= Ph (1), C 6 H 4 F (2) and C 6 H 4 OMe (3) were first synthesized from the polyhydrido copper cluster [Cu 20 H 11 {S 2 P(O i Pr) 2 } 9 ] with nine equiv. of terminal alkynes. Later their isolated yields were significantly improved by direct synthesis from [Cu(CH 3 CN) 4 ](PF 6), [NH 4 ][S 2 P(O i Pr) 2 ], NaBH 4 , and alkynes along with NEt 3 in THF. 1, 2, and 3 were fully characterized by single-crystal X-ray diffraction, ESI-MS and multinuclear NMR spectroscopy. All three clusters have eleven copper atoms adopting 3, 3, 4, 4, 4-pentaccaped trigonal prismatic geometry, with two hydrides inside the Cu 11 cage, the position of which being ascertained by a single-crystal neutron diffraction structure of cluster 1 co-crystallized with a [Cu 7 (H){S 2 P(O i Pr) 2 } 6 ], 4 cluster. Six dithiophosphate and three alkynyl ligands stabilize the Cu 11 H 2 core in which the two hydrides adopt a trigonal pyramidal coordination mode. This coordination mode is so far unprecedented for hydride. The 1 H NMR resonance frequency of the two hydrides appears at 4.8 ppm, a value further confirmed 1 A c c e p t e d m a n u s c r i p t by 2 H NMR spectroscopy for their deuteride derivatives [Cu 11 (D) 2 {S 2 P(O i Pr) 2 } 6 (C≡CR) 3 ]. A DFT investigation allows understanding the bonding within this new type of copper(I) hydrides.

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“…Although several mixed-metal, mixed-valence clusters of the type M II 6 M I 8 (μ 8 -Cl)L 12 are known in the literature, of which copper clusters have been used to elucidate the possible role of d -penicillamine in chemotherapy for Wilson disease, only two halide-centered discrete M 8 cube species, (μ 8 -I)Cd 8 (SCH 2 CH 2 OH) 12 I 3 9c and {Cu 8 (μ 8 -Br)[S 2 P(O i Pr) 2 ] 6 }PF 6 ,9b and one chloride-centered polymeric M 8 cube, {Cu 8 (μ 8 -Cl)[S 2 P(OEt) 2 ] 6 Cl} ∞ , have been identified so far. Our initial report of a bromide-centered Cu I 8 cube having the diselenophosphato ligand (dsep), {Cu 8 (μ 8 -Br)[Se 2 P(O i Pr) 2 ] 6 }(PF 6 ), has been communicated …”

Section: Introductionmentioning

confidence: 99%

Novel Chloride-Centered Discrete Cu^I₈Cubic Clusters Containing Diselenophosphate Ligands. Syntheses and Structures of {Cu₈(μ₈-Cl)[Se₂P(OR)₂]₆}(PF₆) (R = Et, Pr,ⁱPr)¹

et al. 2003

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Three clusters 1-3, Cu(8)(mu8-Cl)[Se(2)P(OR)(2)](6)(PF(6)) (R= Et, Pr, (i)Pr), were synthesized in high yield from the reaction of [Cu(CH(3)CN)(4)](PF(6)), NH(4)[Se(2)P(OR)(2)], and Bu(4)NCl in a molar ratio of 4:3:1 in diethyl ether. FAB mass spectra show m/z peaks at 2218.10 for 1, 2386.10 for 2, and 2387.34 for 3 which are due to molecular cations, [1-PF(6)]+, [2-PF(6)]+, and [3-PF(6)]+, respectively. (31)P NMR spectra of 1-3 display a singlet at delta 76.48, 76.73, and 69.32 ppm with satellites (J(PSe) = 652, 653, and 648 Hz), respectively. The (77)Se NMR spectra of 1-3 exhibit a doublet peak at -21.7, -16.42, and 2.3 ppm, respectively (J(SeP) = 652 Hz for 1, 653 Hz for 2, and 648 Hz for 3). The X-ray structure (1-3) consists of a discrete cationic cluster in which eight copper ions are linked by six diselenophosphate ligands and a central mu8-Cl ion with a noncoordinating PF(6)(-) anion. The shape of the molecule is a chloride-centered distorted Cu(8) cube in clusters 1 and 2 and a near perfect Cu(8) cube for cluster 3. The dsep ligand exhibits a tetrametallic tetraconnective (mu2, mu2)) coordination pattern, and each occupies a square face of the cube. Each copper atom of the cube is coordinated by three selenium atoms with a strong interaction with the central chloride ion. The observed Cu-Cl distances lie in the range 2.649-2.878 A.

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A novel nonacoordinate bridging selenido ligand in a tricapped trigonal-prismatic geometry. X-Ray structure of Cu11(μ9-Se)(μ3-Br)3[Se2P(OPri)2]6

Cited by 36 publications

References 13 publications

Syntheses, Structures, and VT NMR Studies of Diselenophosphates of Group 14 Organometals. DFT Calculations for Gas-Phase Stability of Dinuclear Ions, [(Ph₃M)₂{μ-Se, Se-P(OR)₂}]⁺(M = Ge, Sn, and Pb)

Syntheses, Structures, and VT NMR Studies of Diselenophosphates of Group 14 Organometals. DFT Calculations for Gas-Phase Stability of Dinuclear Ions, [(Ph₃M)₂{μ-Se, Se-P(OR)₂}]⁺(M = Ge, Sn, and Pb)

Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry

Novel Chloride-Centered Discrete Cu^I₈Cubic Clusters Containing Diselenophosphate Ligands. Syntheses and Structures of {Cu₈(μ₈-Cl)[Se₂P(OR)₂]₆}(PF₆) (R = Et, Pr,ⁱPr)¹

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A novel nonacoordinate bridging selenido ligand in a tricapped trigonal-prismatic geometry. X-Ray structure of Cu11(μ9-Se)(μ3-Br)3[Se2P(OPri)2]6

Cited by 36 publications

References 13 publications

Syntheses, Structures, and VT NMR Studies of Diselenophosphates of Group 14 Organometals. DFT Calculations for Gas-Phase Stability of Dinuclear Ions, [(Ph3M)2{μ-Se, Se-P(OR)2}]+(M = Ge, Sn, and Pb)

Syntheses, Structures, and VT NMR Studies of Diselenophosphates of Group 14 Organometals. DFT Calculations for Gas-Phase Stability of Dinuclear Ions, [(Ph3M)2{μ-Se, Se-P(OR)2}]+(M = Ge, Sn, and Pb)

Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry

Novel Chloride-Centered Discrete CuI8Cubic Clusters Containing Diselenophosphate Ligands. Syntheses and Structures of {Cu8(μ8-Cl)[Se2P(OR)2]6}(PF6) (R = Et, Pr,iPr)1

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Syntheses, Structures, and VT NMR Studies of Diselenophosphates of Group 14 Organometals. DFT Calculations for Gas-Phase Stability of Dinuclear Ions, [(Ph₃M)₂{μ-Se, Se-P(OR)₂}]⁺(M = Ge, Sn, and Pb)

Syntheses, Structures, and VT NMR Studies of Diselenophosphates of Group 14 Organometals. DFT Calculations for Gas-Phase Stability of Dinuclear Ions, [(Ph₃M)₂{μ-Se, Se-P(OR)₂}]⁺(M = Ge, Sn, and Pb)

Novel Chloride-Centered Discrete Cu^I₈Cubic Clusters Containing Diselenophosphate Ligands. Syntheses and Structures of {Cu₈(μ₈-Cl)[Se₂P(OR)₂]₆}(PF₆) (R = Et, Pr,ⁱPr)¹