pentaatomic tetracoordinate planar carbon, [cal4]2−: a new structural unit and its salt complexes

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COMMUNICATIONS 3630 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000 1433-7851/00/3920-3630 $ 17.50+.50/0 Angew. Chem. Int. Ed. 2000, 39, No. 20 Pentaatomic Tetracoordinate Planar Carbon, [CAl 4 ] 2 : A New Structural Unit and Its Salt Complexes** Xi Li, Hai-Feng Zhang, Lai-Sheng Wang,* Grant D. Geske, and Alexander I. Boldyrev* Since the pioneering theoretical formulation of hypothet- ical tetracoordinate planar carbon (TPC) molecules by Hoffmann et al. thirty years ago, [1] there have been substantial research efforts to design new molecules that may contain tetracoordinate planar carbon. [2±13] Schleyer et al. [2±4] compu- tationally tested and predicted a wide variety of candidate molecules for TPC, many of which were reviewed recently. [4] Keese et al. [6, 7] performed calculations on promising candi- dates and synthesized many such molecules. Radom et al. [8, 9] performed calculations on a class of polycyclic hydrocarbons, called alkaplanes, in which TPC can be achieved by steric constraints. A divanadium complex, characterized structurally by Cotton and Millar, [10] is probably the first compound with a TPC atom. A variety of organometallic compounds, mostly containing elements of Groups 4 and 5, have since been reported by Erker, Gleiter, and co-workers to contain TPC. [11±13] Our efforts to design new TPC molecules have concen- trated on small five-atom species, the smallest molecules that can contain a TPC atom, in which the bonding of the central carbon atom to its four ligands can be easily traced. Furthermore, planarity in these species is not enforced by their molecular architecture, but rather by their intrinsic and unique electronic structure. On the basis of a simple molecular orbital picture, we found a general rule for achieving planarity in pentaatomic species composed of a first-row central atom and four second- or third-row ligand atoms: such species should possess 17 or 18 valence elec- trons. [14±16] Planarity of these species is achieved through a four-center peripheral ligand ± ligand bonding interaction in their highest occupied molecular orbital (HOMO). Here we discuss the possibility of designing new materials containing such pentaatomic TPC species as building blocks for bulk solid materials. We previously established that the 17- valence-electron CAl 4 is a TPC molecule [16] in which the ligand ± ligand bonding HOMO is singly occupied. When the extra electron is detached, the 16-valence-electron neutral CAl 4 becomes tetrahedral. The CAl 4 ion, with its open electronic shell, is thus expected to be able to accept one more electron into its four-center ligand ± ligand bonding HOMO to generate the closed-shell, 18-valence-electron dianion CAl 4 2 . However, this doubly charged anion is not expected to be stable towards electron autodetachment in its isolated state due to strong Coulomb repulsion between the two extra electrons, analogous to the sulfate dianion SO 4 2 , which is well known to be unstable in the gas phase. [17] One strategy to stabilize such a dianion is to provide it with a counterion, as we observed recently in a series of stable M [SO 4 2 ] species. [18] Here we report the first experimental realization of such a salt-stabilized TPC dianion, namely, Na [CAl 4 2 ], and a theoretical investigation of this anion and the neutral (Na ) 2 [CAl 4 2 ] species. We confirm that the TPC species CAl 4 2 can indeed maintain its structural integrity in the presence of one or two countercations. These findings represent the first step towards the realization of bulk materials based on crystal structural units containing the TPC dianion [CAl 4 2 ] as a novel building block. The experiment was performed with a magnetic-bottle photoelectron spectroscopy apparatus equipped with a laser vaporization source. [19] We made NaCAl 4 by laser vapor- ization of an Al/C/Na composite target containing 75 % Al, 5% C, and 20% NaI by weight. Various Al x C y species and clusters containing Na and I were observed and analyzed by a time-of-flight mass spectrometer. The NaCAl 4 ions were mass-selected and detached by a laser beam in the interaction zone of the magnetic-bottle photoelectron analyzer. Photo- electron spectra were measured at two detachment photon energies, 355 nm (3.496 eV) and 266 nm (4.661 eV), as shown in Figure 1. The electron energy resolution was better than 30 meV for 1 eVelectrons. In the theoretical investigation, [20, 21] we studied extensively possible structures for Na [CAl 4 2 ] and (Na ) 2 [CAl 4 2 ]. At the B3LYP/6-311 G* level of theory, the most stable structure for Na [CAl 4 2 ] was found to be planar with coordination of Na to an edge of CAl 4 2 (Figure 2a). Two other structures, in which Na is coordinated to a corner Al atom or directly to the C atom to form a square pyramid are first- and second-order saddle points lying 14.5 and 12.1 kcal mol 1 higher in energy than the bidentate global- minimum structure, respectively. There is, however, another local minimum corresponding to a structure (Figure 2 b), which can be viewed as exchanging the positions of Na and one of the corner Al atoms in the ground-state structure. This isomer is 25.4 kcal mol 1 higher in energy. When we ex- changed Na and one of the bridged Al atoms in the ground- state structure, the resulting species collapsed into the global minimum upon optimization. For (Na ) 2 [CAl 4 2 ], the most stable structure is also planar with coordination of the two Na ions to opposite edges of CAl 4 2 (Figure 2c). We found another low-lying stable isomer, which is also planar, but in [*] Prof. Dr. A. I. Boldyrev, G. D. Geske Department of Chemistry and Biochemistry Utah State University Logan, UT 84322 (USA) Fax: ( 1) 435-797-3390 E-mail : [email protected] Prof. Dr. L.-S. Wang, [] X. Li, [] Dr. H.-F. Zhang [] Department of Physics, Washington State University 2710 University Drive, Richland, WA 99352 (USA) E-mail: [email protected] [ ] W. R. Wiley Environmental Molecular Sciences Laboratory Pacific Northwest National Laboratory MS K8-88, P. O. Box 999, Richland, WA 99352 (USA) Fax: ( 1) 509-376-6066 [**] The theoretical work was done at Utah State University and supported by the donors of The Petroleum Research Fund (ACS- PRF no. 35255-AC6), administered by the American Chemical Society. The experimental work was supported by the National Science Foundation (DMR-9622733) and performed at the W. R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by DOEs Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory, which is operated for DOE by Battelle. L.S.W. is an AlfredP. Sloan Foundation Research Fellow.

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