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Tris(pyrazol­yl)borate complexes of rhodium are well known to activate C-H bonds. The reactive [Tp'Rh(PMe3)] fragment [Tp' is tris­(3,5-di­methyl­pyrazol-1-yl)hydro­borate] is found to react with valero­nitrile to give the [kappa]1N-bound com­plex (penta­nenitrile-[kappa]N)(tri­methyl­phosphane-[kappa]P)[tris­(3,5-di­methyl­imid­a­zol-1-yl)hydro­borato-[kappa]2N2,N2']rhodium(I), [Rh(C15H22BN6)(C5H9N)(C3H9P)]. In con­trast to the widespread evidence for the reaction of this fragment with C-H bonds via oxidative addition, no evidence for such a complex is observed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616006859/yp3115sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229616006859/yp3115Isup2.hkl
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229616006859/yp3115sup3.pdf
NMR spectra and Xray tables

CCDC reference: 1451243

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

(Pentanenitrile-κN)(trimethylphosphane-κP)[tris(3,5-dimethylimidazol-1-yl)hydroborato-κ2N2,N2']rhodium(I) top
Crystal data top
[Rh(C15H22BN6)(C5H9N)(C3H9P)]F(000) = 584
Mr = 559.31Dx = 1.377 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 8.4544 (8) ÅCell parameters from 4074 reflections
b = 15.0084 (14) Åθ = 2.4–27.9°
c = 10.6904 (10) ŵ = 0.72 mm1
β = 95.975 (2)°T = 100 K
V = 1349.1 (2) Å3Needle, yellow
Z = 20.18 × 0.16 × 0.10 mm
Data collection top
Bruker SMART APEXII CCD Platform
diffractometer
12861 independent reflections
Radiation source: fine-focus sealed tube9022 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.088
ω scansθmax = 36.3°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
h = 1414
Tmin = 0.697, Tmax = 0.747k = 2424
36418 measured reflectionsl = 1717
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.053H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096 w = 1/[σ2(Fo2) + (0.0278P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
12861 reflectionsΔρmax = 1.25 e Å3
313 parametersΔρmin = 1.02 e Å3
1 restraintAbsolute structure: Refined as an inversion twin.
Primary atom site location: difference Fourier mapAbsolute structure parameter: 0.05 (3)
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component racemic twin (95:05).

The borohydride hydrogen atom was found from the difference Fourier map and refined freely.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Rh10.54121 (3)0.29151 (2)0.19412 (3)0.01279 (6)
P10.62592 (10)0.29078 (15)0.39694 (8)0.01597 (18)
N10.3661 (4)0.3823 (3)0.2105 (3)0.0152 (7)
N20.2113 (4)0.3587 (3)0.1738 (3)0.0134 (7)
N30.4300 (4)0.2737 (2)0.0110 (3)0.0146 (9)
N40.2686 (4)0.2579 (2)0.0015 (3)0.0133 (7)
N50.1479 (4)0.2047 (3)0.3221 (3)0.0171 (7)
N60.2036 (4)0.1921 (3)0.2080 (3)0.0135 (7)
B10.1715 (5)0.2677 (3)0.1112 (4)0.0136 (9)
H10.045 (5)0.270 (3)0.077 (4)0.014 (12)*
C10.3653 (5)0.4672 (3)0.2464 (4)0.0179 (9)
C20.2099 (6)0.4993 (3)0.2365 (4)0.0179 (9)
H20.17600.55720.25790.021*
C30.1149 (5)0.4291 (3)0.1891 (4)0.0164 (8)
C40.4788 (5)0.2620 (3)0.1021 (4)0.0150 (8)
C50.3501 (5)0.2392 (3)0.1891 (4)0.0163 (8)
H50.35250.22710.27610.020*
C60.2198 (5)0.2378 (3)0.1228 (4)0.0153 (8)
C70.1777 (5)0.1299 (3)0.3865 (4)0.0170 (9)
C80.2532 (5)0.0677 (3)0.3156 (4)0.0188 (9)
H80.28680.00930.34020.023*
C90.2687 (5)0.1092 (3)0.2019 (4)0.0161 (8)
C100.5160 (6)0.5158 (3)0.2847 (5)0.0237 (10)
H10A0.60650.47570.27880.036*
H10B0.51610.53660.37160.036*
H10C0.52470.56700.22890.036*
C110.0614 (5)0.4267 (3)0.1542 (5)0.0226 (10)
H11A0.10550.37300.18940.034*
H11B0.08390.42600.06240.034*
H11C0.11000.47960.18800.034*
C120.6488 (5)0.2760 (3)0.1241 (4)0.0194 (12)
H12A0.70930.29590.04590.029*
H12B0.65510.32130.18940.029*
H12C0.69350.21990.15140.029*
C130.0498 (5)0.2184 (3)0.1673 (4)0.0216 (10)
H13A0.01110.17020.11690.032*
H13B0.04120.20050.25590.032*
H13C0.01430.27200.15840.032*
C140.1313 (6)0.1221 (4)0.5176 (4)0.0253 (11)
H14A0.08040.17760.54060.038*
H14B0.22630.11120.57620.038*
H14C0.05670.07250.52170.038*
C150.3348 (5)0.0712 (3)0.0891 (4)0.0184 (9)
H15A0.25450.07490.01620.028*
H15B0.36380.00870.10500.028*
H15C0.42930.10500.07200.028*
N70.7006 (4)0.2004 (3)0.1645 (3)0.0155 (7)
C160.7795 (5)0.1432 (3)0.1411 (4)0.0174 (9)
C170.8701 (5)0.0629 (3)0.1141 (4)0.0203 (9)
H17A0.96570.05810.17560.024*
H17B0.90560.06760.02900.024*
C180.7669 (6)0.0202 (3)0.1216 (5)0.0228 (10)
H18A0.67480.01620.05660.027*
H18B0.82970.07330.10280.027*
C190.7058 (6)0.0326 (3)0.2501 (4)0.0217 (10)
H19A0.62630.08120.24420.026*
H19B0.65140.02270.27230.026*
C200.8370 (6)0.0544 (4)0.3549 (5)0.0321 (13)
H20A0.79130.05820.43530.048*
H20B0.91800.00750.35960.048*
H20C0.88580.11160.33700.048*
C210.6523 (7)0.1787 (3)0.4612 (4)0.0265 (11)
H21B0.68290.18220.55210.040*
H21C0.73590.14800.42090.040*
H21D0.55240.14560.44530.040*
C220.8158 (6)0.3405 (4)0.4571 (5)0.0265 (11)
H22A0.83220.33310.54860.040*
H22D0.81490.40410.43630.040*
H22B0.90210.31100.41860.040*
C230.4891 (6)0.3367 (4)0.5005 (5)0.0264 (11)
H23D0.52650.32210.58790.040*
H23A0.38300.31130.47890.040*
H23B0.48420.40160.49050.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Rh10.01127 (11)0.01270 (12)0.01410 (11)0.0004 (2)0.00014 (8)0.0007 (2)
P10.0157 (4)0.0171 (4)0.0146 (4)0.0007 (9)0.0008 (3)0.0004 (9)
N10.0128 (16)0.0155 (19)0.0172 (17)0.0002 (14)0.0007 (13)0.0003 (14)
N20.0102 (16)0.0153 (19)0.0152 (17)0.0005 (14)0.0032 (13)0.0014 (14)
N30.0117 (14)0.016 (3)0.0159 (15)0.0010 (12)0.0004 (11)0.0009 (12)
N40.0099 (15)0.0144 (16)0.0154 (16)0.0023 (12)0.0008 (12)0.0001 (12)
N50.0174 (18)0.0188 (19)0.0152 (17)0.0001 (15)0.0023 (14)0.0000 (14)
N60.0145 (17)0.0137 (19)0.0127 (17)0.0021 (15)0.0031 (13)0.0004 (14)
B10.0112 (19)0.013 (2)0.017 (2)0.0015 (15)0.0028 (16)0.0012 (15)
C10.021 (2)0.014 (2)0.018 (2)0.0005 (17)0.0000 (17)0.0005 (16)
C20.020 (2)0.010 (2)0.024 (2)0.0044 (17)0.0045 (18)0.0004 (17)
C30.015 (2)0.016 (2)0.018 (2)0.0033 (17)0.0034 (16)0.0023 (16)
C40.0121 (18)0.0151 (19)0.0175 (19)0.0002 (14)0.0003 (15)0.0018 (14)
C50.016 (2)0.018 (2)0.0146 (19)0.0006 (17)0.0012 (15)0.0008 (16)
C60.018 (2)0.013 (2)0.0141 (18)0.0020 (16)0.0016 (15)0.0007 (15)
C70.016 (2)0.019 (2)0.0153 (19)0.0017 (17)0.0000 (15)0.0024 (16)
C80.017 (2)0.017 (2)0.022 (2)0.0006 (17)0.0013 (17)0.0047 (18)
C90.013 (2)0.012 (2)0.022 (2)0.0027 (16)0.0017 (17)0.0010 (17)
C100.022 (2)0.015 (2)0.033 (3)0.0024 (18)0.001 (2)0.0050 (19)
C110.014 (2)0.022 (2)0.032 (3)0.0043 (18)0.0029 (18)0.002 (2)
C120.0152 (17)0.023 (4)0.0200 (18)0.0018 (17)0.0027 (14)0.0004 (17)
C130.017 (2)0.031 (3)0.016 (2)0.0037 (19)0.0017 (16)0.0051 (19)
C140.029 (3)0.029 (3)0.017 (2)0.001 (2)0.0012 (19)0.0035 (19)
C150.020 (2)0.012 (2)0.024 (2)0.0011 (17)0.0057 (17)0.0025 (17)
N70.0137 (17)0.0175 (19)0.0150 (17)0.0001 (14)0.0004 (13)0.0028 (14)
C160.016 (2)0.017 (2)0.019 (2)0.0025 (17)0.0005 (16)0.0009 (16)
C170.017 (2)0.019 (2)0.025 (2)0.0032 (18)0.0050 (18)0.0032 (18)
C180.027 (2)0.012 (2)0.029 (2)0.0010 (18)0.0007 (19)0.0048 (18)
C190.020 (2)0.016 (2)0.029 (2)0.0069 (18)0.0005 (18)0.0001 (18)
C200.027 (3)0.036 (3)0.032 (3)0.009 (2)0.002 (2)0.008 (2)
C210.036 (3)0.021 (2)0.021 (2)0.001 (2)0.002 (2)0.0041 (19)
C220.022 (2)0.033 (3)0.022 (2)0.005 (2)0.0056 (19)0.002 (2)
C230.025 (2)0.032 (3)0.023 (2)0.005 (2)0.0068 (19)0.000 (2)
Geometric parameters (Å, º) top
Rh1—N12.033 (4)C10—H10C0.9800
Rh1—N71.968 (4)C11—H11A0.9800
Rh1—N32.098 (3)C11—H11B0.9800
Rh1—P12.2116 (9)C11—H11C0.9800
N7—C161.131 (6)C12—H12A0.9800
P1—C231.818 (5)C12—H12B0.9800
P1—C211.822 (5)C12—H12C0.9800
P1—C221.825 (5)C13—H13A0.9800
N1—C11.330 (6)C13—H13B0.9800
N1—N21.373 (5)C13—H13C0.9800
N2—C31.355 (6)C14—H14A0.9800
N2—B11.543 (6)C14—H14B0.9800
N3—C41.329 (5)C14—H14C0.9800
N3—N41.377 (5)C15—H15A0.9800
N4—C61.354 (5)C15—H15B0.9800
N4—B11.534 (6)C15—H15C0.9800
N5—C71.328 (6)C16—C171.472 (7)
N5—N61.365 (5)C17—C181.530 (7)
N6—C91.366 (6)C17—H17A0.9900
N6—B11.540 (6)C17—H17B0.9900
B1—H11.10 (4)C18—C191.527 (7)
C1—C21.392 (6)C18—H18A0.9900
C1—C101.488 (6)C18—H18B0.9900
C2—C31.388 (6)C19—C201.528 (6)
C2—H20.9500C19—H19A0.9900
C3—C111.499 (6)C19—H19B0.9900
C4—C51.399 (6)C20—H20A0.9800
C4—C121.495 (6)C20—H20B0.9800
C5—C61.371 (6)C20—H20C0.9800
C5—H50.9500C21—H21B0.9800
C6—C131.495 (6)C21—H21C0.9800
C7—C81.397 (6)C21—H21D0.9800
C7—C141.499 (6)C22—H22A0.9800
C8—C91.384 (6)C22—H22D0.9800
C8—H80.9500C22—H22B0.9800
C9—C151.494 (6)C23—H23D0.9800
C10—H10A0.9800C23—H23A0.9800
C10—H10B0.9800C23—H23B0.9800
N7—Rh1—N1175.08 (15)H11A—C11—H11C109.5
N7—Rh1—N390.55 (14)H11B—C11—H11C109.5
N1—Rh1—N384.61 (13)C4—C12—H12A109.5
N7—Rh1—P189.83 (11)C4—C12—H12B109.5
N1—Rh1—P194.77 (11)H12A—C12—H12B109.5
N3—Rh1—P1169.05 (10)C4—C12—H12C109.5
C23—P1—C21100.5 (2)H12A—C12—H12C109.5
C23—P1—C22102.8 (2)H12B—C12—H12C109.5
C21—P1—C22100.1 (2)C6—C13—H13A109.5
C23—P1—Rh1115.69 (17)C6—C13—H13B109.5
C21—P1—Rh1112.88 (18)H13A—C13—H13B109.5
C22—P1—Rh1121.76 (17)C6—C13—H13C109.5
C1—N1—N2107.2 (4)H13A—C13—H13C109.5
C1—N1—Rh1133.8 (3)H13B—C13—H13C109.5
N2—N1—Rh1118.9 (3)C7—C14—H14A109.5
C3—N2—N1109.4 (4)C7—C14—H14B109.5
C3—N2—B1129.5 (4)H14A—C14—H14B109.5
N1—N2—B1120.7 (4)C7—C14—H14C109.5
C4—N3—N4106.7 (3)H14A—C14—H14C109.5
C4—N3—Rh1135.5 (3)H14B—C14—H14C109.5
N4—N3—Rh1117.1 (2)C9—C15—H15A109.5
C6—N4—N3109.3 (3)C9—C15—H15B109.5
C6—N4—B1129.8 (3)H15A—C15—H15B109.5
N3—N4—B1120.9 (3)C9—C15—H15C109.5
C7—N5—N6106.4 (4)H15A—C15—H15C109.5
N5—N6—C9110.3 (4)H15B—C15—H15C109.5
N5—N6—B1116.4 (4)C16—N7—Rh1172.8 (4)
C9—N6—B1133.1 (4)N7—C16—C17174.4 (5)
N4—B1—N6112.7 (3)C16—C17—C18110.2 (4)
N4—B1—N2108.4 (3)C16—C17—H17A109.6
N6—B1—N2110.2 (3)C18—C17—H17A109.6
N4—B1—H1109 (2)C16—C17—H17B109.6
N6—B1—H1110 (2)C18—C17—H17B109.6
N2—B1—H1106 (2)H17A—C17—H17B108.1
N1—C1—C2110.0 (4)C19—C18—C17113.2 (4)
N1—C1—C10121.2 (4)C19—C18—H18A108.9
C2—C1—C10128.7 (4)C17—C18—H18A108.9
C3—C2—C1105.7 (4)C19—C18—H18B108.9
C3—C2—H2127.1C17—C18—H18B108.9
C1—C2—H2127.1H18A—C18—H18B107.7
N2—C3—C2107.6 (4)C18—C19—C20113.4 (4)
N2—C3—C11123.1 (4)C18—C19—H19A108.9
C2—C3—C11129.2 (4)C20—C19—H19A108.9
N3—C4—C5110.1 (4)C18—C19—H19B108.9
N3—C4—C12121.3 (4)C20—C19—H19B108.9
C5—C4—C12128.6 (4)H19A—C19—H19B107.7
C6—C5—C4105.7 (4)C19—C20—H20A109.5
C6—C5—H5127.1C19—C20—H20B109.5
C4—C5—H5127.1H20A—C20—H20B109.5
N4—C6—C5108.1 (4)C19—C20—H20C109.5
N4—C6—C13122.4 (4)H20A—C20—H20C109.5
C5—C6—C13129.5 (4)H20B—C20—H20C109.5
N5—C7—C8110.8 (4)P1—C21—H21B109.5
N5—C7—C14119.8 (4)P1—C21—H21C109.5
C8—C7—C14129.4 (4)H21B—C21—H21C109.5
C9—C8—C7105.5 (4)P1—C21—H21D109.5
C9—C8—H8127.3H21B—C21—H21D109.5
C7—C8—H8127.3H21C—C21—H21D109.5
N6—C9—C8107.0 (4)P1—C22—H22A109.5
N6—C9—C15125.0 (4)P1—C22—H22D109.5
C8—C9—C15127.9 (4)H22A—C22—H22D109.5
C1—C10—H10A109.5P1—C22—H22B109.5
C1—C10—H10B109.5H22A—C22—H22B109.5
H10A—C10—H10B109.5H22D—C22—H22B109.5
C1—C10—H10C109.5P1—C23—H23D109.5
H10A—C10—H10C109.5P1—C23—H23A109.5
H10B—C10—H10C109.5H23D—C23—H23A109.5
C3—C11—H11A109.5P1—C23—H23B109.5
C3—C11—H11B109.5H23D—C23—H23B109.5
H11A—C11—H11B109.5H23A—C23—H23B109.5
C3—C11—H11C109.5
C1—N1—N2—C30.9 (5)B1—N2—C3—C2172.6 (4)
Rh1—N1—N2—C3178.3 (3)N1—N2—C3—C11178.2 (4)
C1—N1—N2—B1172.5 (4)B1—N2—C3—C115.5 (7)
Rh1—N1—N2—B14.9 (5)C1—C2—C3—N20.9 (5)
C4—N3—N4—C60.8 (4)C1—C2—C3—C11177.1 (5)
Rh1—N3—N4—C6172.9 (3)N4—N3—C4—C50.4 (5)
C4—N3—N4—B1178.5 (3)Rh1—N3—C4—C5170.3 (3)
Rh1—N3—N4—B19.5 (5)N4—N3—C4—C12178.5 (4)
C7—N5—N6—C90.2 (5)Rh1—N3—C4—C1211.6 (6)
C7—N5—N6—B1175.6 (4)N3—C4—C5—C60.1 (5)
C6—N4—B1—N6110.4 (5)C12—C4—C5—C6177.8 (4)
N3—N4—B1—N672.5 (5)N3—N4—C6—C50.9 (5)
C6—N4—B1—N2127.3 (4)B1—N4—C6—C5178.3 (4)
N3—N4—B1—N249.8 (5)N3—N4—C6—C13179.0 (4)
N5—N6—B1—N4167.2 (3)B1—N4—C6—C131.6 (7)
C9—N6—B1—N418.3 (6)C4—C5—C6—N40.6 (5)
N5—N6—B1—N246.0 (5)C4—C5—C6—C13179.3 (5)
C9—N6—B1—N2139.5 (5)N6—N5—C7—C80.0 (5)
C3—N2—B1—N4118.3 (5)N6—N5—C7—C14179.7 (4)
N1—N2—B1—N453.6 (5)N5—C7—C8—C90.1 (5)
C3—N2—B1—N6118.0 (5)C14—C7—C8—C9179.5 (4)
N1—N2—B1—N670.1 (5)N5—N6—C9—C80.2 (5)
N2—N1—C1—C21.5 (5)B1—N6—C9—C8174.5 (4)
Rh1—N1—C1—C2178.3 (3)N5—N6—C9—C15177.2 (4)
N2—N1—C1—C10176.2 (4)B1—N6—C9—C152.4 (8)
Rh1—N1—C1—C100.6 (7)C7—C8—C9—N60.2 (5)
N1—C1—C2—C31.4 (5)C7—C8—C9—C15177.0 (4)
C10—C1—C2—C3176.0 (5)C16—C17—C18—C1959.0 (5)
N1—N2—C3—C20.0 (5)C17—C18—C19—C2067.9 (5)
 

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