desc should be applied on a column not a window definition. You can use either a method on a column:

from pyspark.sql.functions import col, row_number
from pyspark.sql.window import Window

F.row_number().over(
    Window.partitionBy("driver").orderBy(col("unit_count").desc())
)

or a standalone function:

from pyspark.sql.functions import desc
from pyspark.sql.window import Window

F.row_number().over(
    Window.partitionBy("driver").orderBy(desc("unit_count"))
)

Or you can use the SQL code in Spark-SQL:

from pyspark.sql import SparkSession

spark = SparkSession\
    .builder\
    .master('local[*]')\
    .appName('Test')\
    .getOrCreate()

spark.sql("""
    select driver
        ,also_item
        ,unit_count
        ,ROW_NUMBER() OVER (PARTITION BY driver ORDER BY unit_count DESC) AS rowNum
    from data_cooccur
""").show()