Ba<sub>2</sub>NiSi<sub>3</sub>:  A One-Dimensional Solid-State Metallocene Analog

Goodey, Joanna; Mao, Jiang‐Gao; Guloy, Arnold M.

doi:10.1021/ja0016102

Cited by 15 publications

(10 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Copper(II) sites with trigonal‐prismatic geometry can be found in minerals such as lyonsite, buttbengachite, connellite, and claringbullite 73. A review of trigonal‐prismatic oxo‐rhodates can be found in the literature,74 while other examples of metals in trigonal‐prismatic coordination are found in Ba 2 NiSi 3 , NaNbO 2 , and LiNbO 2 75…”

Section: Occurrence and Relevance Of The Trigonal Prism As A Coordinamentioning

confidence: 99%

The Trigonal Prism in Coordination Chemistry

Cremades

Echeverría

Álvarez

2010

Chemistry A European J

View full text Add to dashboard Cite

Herein we analyze the accessibility of the trigonal-prismatic geometry to metal complexes with different electron configurations, as well as the ability of several hexadentate ligands to favor that coordination polyhedron. Our study combines i) a structural database analysis of the occurrence of the prismatic geometry throughout the transition-metal series, ii) a qualitative molecular orbital analysis of the distortions expected for a trigonal-prismatic geometry, and iii) a computational study of complexes of several transition-metal ions with different hexadentate ligands. Also the tendency of specific electron configurations to present a cis bond-stretch Jahn-Teller distortion is analyzed.

show abstract

Section: Occurrence and Relevance Of The Trigonal Prism As A Coordinamentioning

confidence: 99%

The Trigonal Prism in Coordination Chemistry

Cremades

Echeverría

Álvarez

2010

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Due to its filled d 10 orbitals, tolerating diverse coordination patterns, nickel forms a huge number of polar intermetallic compounds in the Ae ‐Ni‐ E systems ( Ae = alkaline‐earth metal, E = Si, Ge) with various different structures . Here the electropositive Ae atom is embedded within a polyanionic [Ni x E y ] z – substructure.…”

Section: Introductionmentioning

confidence: 99%

“…Here the electropositive Ae atom is embedded within a polyanionic [Ni x E y ] z – substructure. Such polyanions can be found for instance in Ba 2 NiSi 3 as [NiSi 3 ] 4– strings or as [NiGe] 2– ribbons in (Sr/Ba)NiGe, which penetrate in one dimension , . With decreasing cation size such [NiGe] 2– ribbons condense into a two‐ or three‐dimensional substructure by forming layers or framework reported for CaNiGe or MgNiGe, respectively , …”

Section: Introductionmentioning

confidence: 99%

SrNi₂Si and BaNi₂Si – New Layered Silicides with Fused Nickel Six‐membered Rings in a Boat Conformation

Braun

Zeitz

Hlukhyy

2019

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

Intermetallic compounds SrNi 2 Si and BaNi 2 Si were prepared by arc-melting of stoichiometric mixture of the elements and subsequent annealing in welded niobium ampoules. Both compounds were investigated by X-ray diffraction on powder as well as single crystal methods. The title compounds both crystallize in the BaNi 2 Ge structure type (space group Pmmn, Z = 2), a ternary ordered variant of TiCu 3 : a = 4.0296(9) Å, b = 6.5121(14) Å, c = 5.6839(21) Å, R 1 = 0.040 for SrNi 2 Si and a = 4.0681(9) Å, b = 6.580(4) Å, c = 5.976(5) Å, R 1 = 0.031 for BaNi 2 Si. The structure contains corrugated polyanionic * Dr. V. Hlukhyy

show abstract

“…At the other extreme are the Hume-Rothery phases in which the low Δχ and χ values result in the vanishing of clear charge assignments or localized bonds [3]. The divide between the Zintl and Hume-Rothery has inspired the synthetic probing of their border for new phases with unique bonding and structures [4][5][6][7][8][9][10][11][12][13][14][15][16][17]. A rich structural chemistry of polar intermetallic phases has resulted, which offers opportunities to chart how the close-shell electron configurations of the Zintl phases map to the delocalized bonding of the Hume-Rothery phases.…”

Section: Introductionmentioning

confidence: 99%

Bonding Schemes for Polar Intermetallics through Molecular Orbital Models: Ca-Supported Pt–Pt Bonds in Ca10Pt7Si3

et al. 2013

View full text Add to dashboard Cite

Exploratory synthesis in the area of polar intermetallics has yielded a rich variety of structures that offer clues into the transition in bonding between Zintl and Hume-Rothery phases. In this article, we present a bonding analysis of one such compound, Ca 10 Pt 7 Si 3 , whose large Ca content offers the potential for negative formal oxidation states on the Pt. The structure can be divided into a sublattice of Ca cations and a Pt-Si polyanionic network built from Pt 7 Si 3 trefoil units linked through Pt-Pt contacts of 3.14 Å. DFT-calibrated Hückel models reveal that the compound adheres well to a Zintl-like electron counting scheme, in which the Pt-Si and Pt-Pt contacts are equated with two-center two-electron bonds. The experimental electron count is in excess of that predicted by 2%, a discrepancy which is attributed to the electron transfer from the Ca to the Pt-Si network being incomplete. For the Pt-Pt contacts, the occupancy of the bonding orbitals is dependent on the participation of the surrounding Ca atoms in bridging interactions. This use of multi-center interactions isolobal to classical two-center two-electron bonds may illustrate one path by which the bonds delocalize as one moves from the Zintl phases toward the Hume-Rothery domain.

show abstract

Ba₂NiSi₃: A One-Dimensional Solid-State Metallocene Analog

Cited by 15 publications

References 27 publications

The Trigonal Prism in Coordination Chemistry

The Trigonal Prism in Coordination Chemistry

SrNi₂Si and BaNi₂Si – New Layered Silicides with Fused Nickel Six‐membered Rings in a Boat Conformation

Bonding Schemes for Polar Intermetallics through Molecular Orbital Models: Ca-Supported Pt–Pt Bonds in Ca10Pt7Si3

Contact Info

Product

Resources

About

Ba2NiSi3: A One-Dimensional Solid-State Metallocene Analog

Cited by 15 publications

References 27 publications

The Trigonal Prism in Coordination Chemistry

The Trigonal Prism in Coordination Chemistry

SrNi2Si and BaNi2Si – New Layered Silicides with Fused Nickel Six‐membered Rings in a Boat Conformation

Bonding Schemes for Polar Intermetallics through Molecular Orbital Models: Ca-Supported Pt–Pt Bonds in Ca10Pt7Si3

Contact Info

Product

Resources

About

Ba₂NiSi₃: A One-Dimensional Solid-State Metallocene Analog

SrNi₂Si and BaNi₂Si – New Layered Silicides with Fused Nickel Six‐membered Rings in a Boat Conformation