Another rule-breaker. Characterization of the unusual cobalt carbonyl borane Co5(CO)13(.mu.-CO)B2H

Jun, Chang Soo; Fehlner, Thomas P.; Rheingold, Arnold L.

doi:10.1021/ja00063a080

Cited by 14 publications

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“…h (1.80(2) Å) and [Co 5 (CO) 14 B(BH)] (1.85(4) Å). 30,31 The FeÀB1 distances 34 The FeÀSe distances (2.3665 (11) and 2.3977(11) Å) are slightly longer than the ironÀselenium cubane cluster [(CpFe) 4 Se 4 ](PF 6 ) 3 (2.3305 Å). 35 The average bond length of MoÀSe is 2.4302 Å, 0.14 Å longer than that observed in the cubane-like compound [MoAg 3 Se 3 Br].…”

Section: ' Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Electronic Structure of New Type of Heterometallic Boride Clusters

et al. 2011

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The reaction of [Cp*TaCl(4)], 1 (Cp* = η(5)-C(5)Me(5)), with [LiBH(4)·THF] at -78 °C, followed by thermolysis in the presence of excess [BH(3)·THF], results in the formation of the oxatantalaborane cluster [(Cp*Ta)(2)B(4)H(10)O], 2 in moderate yield. Compound 2 is a notable example of an oxatantalaborane cluster where oxygen is contiguously bound to both the metal and boron. Upon availability of 2, a room temperature reaction was performed with [Fe(2)(CO)(9)], which led to the isolation of [(Cp*Ta)(2)B(2)H(4)O{H(2)Fe(2)(CO)(6)BH}], 3. Compound 3 is an unusual heterometallic boride cluster in which the [Ta(2)Fe(2)] atoms define a butterfly framework with one boron atom lying in a semi-interstitial position. Likewise, the diselenamolybdaborane, [(Cp*Mo)(2)B(4)H(4)Se(2)], 4 was treated with an excess of [Fe(2)(CO)(9)] to afford the heterometallic boride cluster [(Cp*MoSe)(2)Fe(6)(CO)(13)B(2)(BH)(2)], 5. The cluster core of 5 consists of a cubane [Mo(2)Se(2)Fe(2)B(2)] and a tricapped trigonal prism [Fe(6)B(3)] fused together with four atoms held in common between the two subclusters. In the tricapped trigonal prism subunit, one of the boron atoms is completely encapsulated and bonded to six iron and two boron atoms. Compounds 2, 3, and 5 have been characterized by mass spectrometry, IR, (1)H, (11)B, (13)C NMR spectroscopy, and the geometric structures were unequivocally established by crystallographic analysis. The density functional theory calculations yielded geometries that are in close agreement with the observed structures. Furthermore, the calculated (11)B NMR chemical shifts also support the structural characterization of the compounds. Natural bond order analysis and Wiberg bond indices are used to gain insight into the bonding patterns of the observed geometries of 2, 3, and 5.

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Section: ' Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Electronic Structure of New Type of Heterometallic Boride Clusters

et al. 2011

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“…SMe 2 and Co 2 (CO) 8 was rationalized using s-bond metathesis of the B-H bond as an essential feature of the cluster building reaction. 4,5 However, this metallaborane, and an intermediate compound, Co 2 -(CO) 6 B 2 H 4 , were only isolated in low yields partly due to efficient competitive formation of Co 4 (CO) 12 . Hence, without confirmation this mechanism remains speculative.…”

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Designer clusters: synthesis and characterization of Cp2Rh2Co3(CO)8B3HCl (Cp =η5-C5Me5)

Lei¹,

Shang²,

Fehlner³

1999

Chem. Commun.

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“…4). In the 'H NMR spectrum (at 298 K, in CD,CI,) compound 2 shows two signals at 6 a rocking process, it is possible that in solution the AuPPh, unit bridges the Rh-B edge rather than capping the Ru(l), Rh, B face as in the solid state; the effect on the nbd protons is the same as in the proposed dynamic process.] Fig.…”

Section: Solution Dynamics Of [Rhruh(nbd)(co)b(aupr)i (R = Ph Ch or 2...mentioning

confidence: 82%

“…The reaction of [RuH,(CO),,BH] -with 1 equivalent of [{Rh(q5-C,Me,)C12)2] yielded compound 1 as the only characterisable product. In the "B NMR spectrum a signal at 6 + 155 suggests that the environment about the boron atom may be intermediate between that of a neutral M4B butterfly (semi-interstitial, typically 6 z 110) and a M,B cage (interstitial, typically 6 z 195-200). '.2 In the 'H NMR spectrum a singlet at 6 + 1.78 is consistent with the presence of the C5Me, ligand, whilst a sharp singlet and a broad resonance at F -18.60 and -5.6, respectively, are indicative of Ru-H-Ru and Ru-H-B protons respectively.…”

Section: Synthesis and Spectroscopic Characterisation Of [ Rhru4hz(qs-mentioning

confidence: 99%

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Cluster core geometrical variation in heterometallic boride clusters containing RhRu₄skeletons: crystal structures of [RhRu₄H₂(η⁵-C₅Me₅)(µ-Cl)(CO)₁₂B] and [RhRu₄H(nbd)(CO)₁₂B(AuPPh₃)](nbd = norbornadiene)

Hattersley¹,

Housecroft²,

Rheingold³

1996

J. Chem. Soc., Dalton Trans.

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The reaction of the butterfly anion [Ru,H(CO),,BH] -with [{Rh(q5-C,Me5)CI,},] gave the novel boroncontaining cluster [RhRu,H,(q 5-C,Me,)(p-CI)(CO), ,B] which has been characterised spectroscopically and by X-ray crystallography. Consistent with the 78 valence-electron (v.e.) count, the five metal atoms adopt an open skeletal structure which can be described as an 'envelope' (or an edge-bridged square) geometry. In contrast, when [Ru,H(CO),,BH] -reacted with [(Rh(nbd)CI},] (nbd = norbornadiene) and [Au(PR,)Cl] (R = Ph, C6H1 or 2-MeC6H,), boride clusters containing both RhRu,B and Rh,Ru,B skeletons were obtained. The presence of the gold(1) phosphine is necessary to trap the RhRu,B-containing product. The Rh,Ru,B clusters possess octahedral frameworks and are related to the previously reported [Rh,Ru,(CO), ,B(AuPR,)] compounds. However, the incorporation of only one rhodium fragment leads to the clusters [RhRu,H(nbd)-(CO),,B(AuPR,)], and a square-based pyramidal RhRu, framework (consistent with a 74 v.e. count) has been confirmed by the results of a single-crystal X-ray diffraction study of [RhRu,H(nbd)(CO), ,B(AuPPh,)].

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Another rule-breaker. Characterization of the unusual cobalt carbonyl borane Co5(CO)13(.mu.-CO)B2H

Cited by 14 publications

References 0 publications

Synthesis, Characterization, and Electronic Structure of New Type of Heterometallic Boride Clusters

Synthesis, Characterization, and Electronic Structure of New Type of Heterometallic Boride Clusters

Designer clusters: synthesis and characterization of Cp2Rh2Co3(CO)8B3HCl (Cp =η5-C5Me5)

Cluster core geometrical variation in heterometallic boride clusters containing RhRu₄skeletons: crystal structures of [RhRu₄H₂(η⁵-C₅Me₅)(µ-Cl)(CO)₁₂B] and [RhRu₄H(nbd)(CO)₁₂B(AuPPh₃)](nbd = norbornadiene)

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Another rule-breaker. Characterization of the unusual cobalt carbonyl borane Co5(CO)13(.mu.-CO)B2H

Cited by 14 publications

References 0 publications

Synthesis, Characterization, and Electronic Structure of New Type of Heterometallic Boride Clusters

Synthesis, Characterization, and Electronic Structure of New Type of Heterometallic Boride Clusters

Designer clusters: synthesis and characterization of Cp*2Rh2Co3(CO)8B3HCl (Cp* =η5-C5Me5)

Cluster core geometrical variation in heterometallic boride clusters containing RhRu4skeletons: crystal structures of [RhRu4H2(η5-C5Me5)(µ-Cl)(CO)12B] and [RhRu4H(nbd)(CO)12B(AuPPh3)](nbd = norbornadiene)

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Designer clusters: synthesis and characterization of Cp2Rh2Co3(CO)8B3HCl (Cp =η5-C5Me5)

Cluster core geometrical variation in heterometallic boride clusters containing RhRu₄skeletons: crystal structures of [RhRu₄H₂(η⁵-C₅Me₅)(µ-Cl)(CO)₁₂B] and [RhRu₄H(nbd)(CO)₁₂B(AuPPh₃)](nbd = norbornadiene)