Polyhedral transition metal complexes containing the B9H9CHP2- and B9H9CHPCH3- ligands

Todd, Lee J.; Paul, Iain C.; Little, John L.; Welcker, Peter S.; Peterson, Carlyn R.

doi:10.1021/ja01018a071

Cited by 32 publications

(9 citation statements)

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“…The structure of compound 3‐Cl‐ 2 (Figure 1 top) is consistent with a C s symmetry plane that bisects the P7−P8 bond and intersects the chlorinated B3 vertex together with the bottom B1 atom. The P−P and two P−C bond lengths of 2.1931(9) and 1.865(3), 1.856(3) Å, respectively, are similar to those found for other phosphaborane and phosphacarborane compounds 10, 11. The other P−B, C−B, and B−B (Table 2) separations also fall within the usual limits 1.…”

Section: Resultssupporting

confidence: 78%

Phosphacarborane Chemistry: The 7,8,9,11-, 7,9,8,10- and 7,8,9,10-Isomers ofnido-P2C2B7H9—Diphosphadicarbaborane Analogues of 7,8,9,10-C4B7H11

et al. 2001

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The reaction between the carborane arachno-4,6-C2B7H13 (1) and PCl3 in dichloromethane in the presence of a "proton sponge" (PS = 1,8-dimethylaminonaphthalene) resulted in the isolation of the eleven-vertex nido-diphosphadicarbaboranes 7,8,9,11-P2C2B7H, (2) and 3-Cl-7,8,11-P2C2B7H, (3-Cl-2) in yields of 54 and 7%, respectively. Replacement of the PS by NEt3 in the same reaction gave diphosphadicarbaboranes 2 and 3-CI-2 together with the isomeric species nido-7,9,8,10-P2C2B7H, (3) in yields of 28, 15 and 3%, respectively. The reaction between the isomeric carborane arachno-4,5-C2B7H13 (4) and PCl3 in dichloromethane in the presence of PS gave the asymmetrical isomer, nido-7,8,9,10-P2C2B7H, (5). along with the chloro derivatives 4-Cl-7,8,9,10-P2C2B7H8 (4-Cl-5) and 11-Cl-7,8,9,10-PC2B7,H8 (11-Cl-5) (yields of 21, 1 and 13%, respectively). The structures of the chlorinated derivatives 3-Cl2 and 11 -Cl-5 were determined by X-ray diffraction analysis. In addition, the structures of all compounds isolated were geometry-optimised and confirmed by comparison of experimental 11B chemical shifts with those calculated by the GIAO-SCF/II//RMP2(fc)/6-31G* method. The calculations also include the structure and 11B NMR shifts of the isomer nido-7,10,8,9-P2C2B7H9 (6) which has not yet been isolated.

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Section: Resultssupporting

confidence: 78%

Phosphacarborane Chemistry: The 7,8,9,11-, 7,9,8,10- and 7,8,9,10-Isomers ofnido-P2C2B7H9—Diphosphadicarbaborane Analogues of 7,8,9,10-C4B7H11

et al. 2001

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“…The carbon atoms of the Cp ring are disordered, in contrast with the positions of the twelve‐vertex FePC 2 B 8 H 10 cluster. The FeC(cage) and FeP distances are 2.018(2) Å (mean) and 2.2515(6) Å, respectively, other intracluster CB, PB, and BB distances approximate those found crystallographically12 for the phosphacarbollide complex [Fe(9‐CH 3 ‐9,7‐PCB 9 H 10 ) 2 ]. The structure determination also confirms a symmetrical arrangement of the Fe, C, and P heteroatoms within the 12‐vertex closo cage with a C s symmetry plane bisecting the CC bond and intersecting the P2, B9, and B12 atoms.…”

Section: Resultssupporting

confidence: 62%

Formation of Two Isomeric closo‐[(η⁵‐C₅H₅)FePC₂B₈H₁₀] Phosphadicarbaborane Analogues of Ferrocene via Isolable η¹‐Bonded Complexes of the [7‐{(η⁵‐C₅H₅)Fe(CO)₂}‐(η¹‐nido‐PC₂B₈H₁₀)] Type

Štı́br¹,

Holub²,

Bakardjiev³

et al. 2003

Chemistry A European J

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The reaction of nido-[7,8,9-PC(2)B(8)H(11)] (1) with [[CpFe(CO)(2)](2)] (Cp=eta(5)-C(5)H(5) (-)) in benzene (reflux, 3 days) gave an eta(1)-bonded complex [7-Fp-(eta(1)-nido-7,8,9,-PC(2)B(8)H(10))] (2; Fp=CpFe(CO)(2); yield 38 %). A similar reaction at elevated temperatures (xylene, reflux 24 h) gave the isomeric complex [7-Fp-(eta(1)-nido-7,9,10-PC(2)B(8)H(10))] (3; yield 28 %) together with the fully sandwiched complexes [1-Cp-closo-1,2,4,5-FePC(2)B(8)H(10)] 4 a (yield 30%) and [1-Cp-closo-1,2,4,8-FePC(2)B(8)H(10)] 4 b (yield 5%). Compounds 2 and 3 are isolable intermediates along the full eta(5)-complexation pathway of the phosphadicarbaborane cage; their heating (xylene, reflux, 24 h) leads finally to the isolation of compounds 4 a (yields 46 and 52%, respectively) and 4 b (yields 4 and 5%, respectively). Moreover, compound 3 is isolated as a side product from the heating of 2 (yield 10%). The structure of compound 4 a was determined by an X-ray structural analysis and the constitution of all compounds is consistent with the results of mass spectrometry and IR spectroscopy. Multinuclear ((1)H, (11)B, (31)P, and (13)C), two-dimensional [(11)B-(11)B]-COSY, and (1)H[(11)B(selective)] magnetic resonance measurements led to complete assignments of all resonances and are in excellent agreement with the structures proposed.

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“…The differences in intensities may be due to grinding and packing effects combined with the increase in metal scattering power in going from firstto second-and third-row metals. Another possibility which must, however, be .40 m, 9.02 m, 8.75 m, 8.20 s, 7.70 m, 7.37 vs, 7.13 s, 6.55 w, 6.20 w, 6.10 w, 5.99 w, 5.82 w, 5.64 m, 5.40 s, 5.18 vs, 4.90 w, 4.82 m, 4.66 s, 4.47 s, 4.33 m, 4.19 m, 4.04 vs, 3.91 m, 3.87 w, 3.73 m, 3.64 w, 3.56 w, 3.40 m, 3.32 w considered is that the compounds are indeed isomorphous (that is, they crystallize in the same space group with similar unit cell dimensions) but that the complex anions are in fact not isostructural. This could also account for the observed differences.…”

Section: Resultsmentioning

confidence: 99%

“…the 18-electron ion ( -6)2 2+.3 A phosphacarborane analog of nickelocene, (lT-BgHgCHPCELL Ni, has also been reported. 4 The mixed sandwich molecule (CóH6)Ni(l,2-BgC2Hii) has been prepared and represents an example of a stable 19-electron system.3…”

Section: Discussionmentioning

confidence: 99%

Synthesis and characterization of tris(maleonitriledithiolato)metalates

Stiefel¹,

Bennett²,

Dori³

et al. 1970

Inorg. Chem.

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Polyhedral transition metal complexes containing the B9H9CHP2- and B9H9CHPCH3- ligands

Cited by 32 publications

References 1 publication

Phosphacarborane Chemistry: The 7,8,9,11-, 7,9,8,10- and 7,8,9,10-Isomers ofnido-P2C2B7H9—Diphosphadicarbaborane Analogues of 7,8,9,10-C4B7H11

Phosphacarborane Chemistry: The 7,8,9,11-, 7,9,8,10- and 7,8,9,10-Isomers ofnido-P2C2B7H9—Diphosphadicarbaborane Analogues of 7,8,9,10-C4B7H11

Formation of Two Isomeric closo‐[(η⁵‐C₅H₅)FePC₂B₈H₁₀] Phosphadicarbaborane Analogues of Ferrocene via Isolable η¹‐Bonded Complexes of the [7‐{(η⁵‐C₅H₅)Fe(CO)₂}‐(η¹‐nido‐PC₂B₈H₁₀)] Type

Synthesis and characterization of tris(maleonitriledithiolato)metalates

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Polyhedral transition metal complexes containing the B9H9CHP2- and B9H9CHPCH3- ligands

Cited by 32 publications

References 1 publication

Phosphacarborane Chemistry: The 7,8,9,11-, 7,9,8,10- and 7,8,9,10-Isomers ofnido-P2C2B7H9—Diphosphadicarbaborane Analogues of 7,8,9,10-C4B7H11

Phosphacarborane Chemistry: The 7,8,9,11-, 7,9,8,10- and 7,8,9,10-Isomers ofnido-P2C2B7H9—Diphosphadicarbaborane Analogues of 7,8,9,10-C4B7H11

Formation of Two Isomeric closo‐[(η5‐C5H5)FePC2B8H10] Phosphadicarbaborane Analogues of Ferrocene via Isolable η1‐Bonded Complexes of the [7‐{(η5‐C5H5)Fe(CO)2}‐(η1‐nido‐PC2B8H10)] Type

Synthesis and characterization of tris(maleonitriledithiolato)metalates

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Formation of Two Isomeric closo‐[(η⁵‐C₅H₅)FePC₂B₈H₁₀] Phosphadicarbaborane Analogues of Ferrocene via Isolable η¹‐Bonded Complexes of the [7‐{(η⁵‐C₅H₅)Fe(CO)₂}‐(η¹‐nido‐PC₂B₈H₁₀)] Type